• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Condensation polymers or addition polymers which contain sterically hindered polyalkylpiperidine groups are proposed as light stabilizers for plastics. The polymers concerned are relatively low-molecular polymers and a difunctional derivative of a polyalkylpiperidine is additionally used for the manufacture of these. The piperidine radical can be present in the main chain or as a side group of the polymeric stabilizer. Polymeric stabilizers of this type do not tend to migrate out of the plastic or to be removed by extraction; they are therefore very permanent in use.
    公开号:SU1131472A3
    申请号:SU772480054
    申请日:1977-05-10
    公开日:1984-12-23
    发明作者:Роди Жан；Расбергер Михаэль
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    Where 2-8 and 3,5-16,5, of the general formula
    CHS CHjCiHs. ,
    (-o-co-i-co4-
     Iif)
    CiHs
    . "H" I
    CHj CHj
    CH, SHZ
    about
    ,
    SNS SNZ
    where -h 7
    and the general formula
    Н, СНз СН, СНз о | 0- CHi-CH (M-CHi-KQ..ECHj СНз сНз СНз where Е- (СНд) „„ -CCC, H5) i-, -CHfCHiCeHs) - or-ССС Нс, ), -, tl 2-8 and And 6-12,5
    in the following ratio of komtocetov, mas.n .:
    Polymer 100
    Stabilizer, 0.05-2
    The invention relates to the chemistry of polymers, in particular to polymer compositions containing a stabilizer. Nitrogen-containing tetrocyclic compounds are known to be effective light stabilizers for polymeric materials ClJ. However, these stabilizers are characterized by high volatility. Closest to the proposed technical essence and the effect achieved is a polymer composition containing a polymer, in particular a polyolefin, a homo- or copolymer, styrene, polyester-based polyurethane, polycaproamide, and a stabilizer, a derivative of tetramethyl piperidine 2J. A disadvantage of the known technical solution is the low light resistance of the composition. The purpose of the invention is to increase the light stability of the composition. This goal is achieved by the fact that a polymeric composition containing a polymer selected from the group comprising polyolefin, styrene homo- or copolymer, polyurethane based on polyester and polycarroamide, and a stabilizer, contains a compound selected from the group including polyester common of the formula O O iCH2tm, - O / -rC (C2H5) r, -C () 2 -, - CH (CH2SbN5b chS, C (CH3) s Ur-I | g / - Shg-C-CHaCHO C C (CHj ) 3 С (СНз) з гН5 С-СН29-С - СН2I - С (СНз) з 2-СН (СНз) -СН2-С (СНз) гСНз .Нз В - СН2 СНз СНз СНзСНз -CH-CH2-B CH3 Nz 3 CH, CHj DOOC - -, CHj CH3 SnGsNz 2-8 and h 3,5 - 16,5, of the general formula CHj CH} g v-njQ.j - | -OHQN-CHz - @ - CHz-NQ-0-CO-C-Co4 .CHj CHjCHj HjCzHs CHj CHj where h 9, 5, of the general formula Shz CH3 1 fc-CH. CHz Shz where h 7, and the general formula. Sn about 4-04) N-CHj-CH-Clt-CHi-Tl () - 0-CE-C4 CHj CHjWh CH3 where E- (CHjfri, -C (CzH5) 2.-, -CHfcHiCgHsl-HAM-cfc Hs) and: p 6-12.5 in the following ratio of components, m.ch .: Polymer100 Stabilizer 0.05-2 Stabilization agents can be introduced, for example, by mixing with known methods before or during molding, or by applying a solution or dispersed compounds on the α-polymer, in accordance with the tea, with subsequent removal of the solvent. Polymers stabilized in this way may also contain other stabilizers and conventional additives. When used together, known stabilizers may observe a synergistic effect, which is especially the case when other light-protective means of organic phosphites are combined together. Of particular importance is the combined use of light stabilizers in the stabilization of polyolefins. 724 Example 1. Stabilization of a polypropylene film. 100 ma.ch. polypropylene powder (Maplen Fiber grade company Montedison) homogenized with 0.2 wt.h. octadecyl ester of E- {3,5-di-tert-butyl-4-hydroxy-1) propionic acid and 25 wt. or 0.05 math. one of the table 1 stabilizers in the Brabender plastograph at 200 ° C for 10 minutes. The resulting maesu is possibly removed very quickly from the mixer and pressed into plates with a thickness of 2-3 mm in a cranked press. The nast of the obtained wet pressed mass is cut out and pressed into plates with a thickness of 0.5 mm between two highly polished plates of solid aluminum using a manual hydraulic laboratory press for 6 minutes at a pressure of 260 t at 260 C, and then poured with cold water. From this film with a thickness of 0.5 mm, under the same conditions, a test film with a thickness of 0.1 mm is obtained, from which suitable samples are drawn and irradiated in a xenotest 150 or in a xenotest 1200. At equal intervals of time, these samples are removed from the xenotest and tested for carbonyl content in IR spectrophotometer at 5.85 i. The increase in carbonyl extinction upon irradiation is a measure of the photo-oxidative decomposition of the polymer and is associated with a decrease in the mechanical properties of the polymer. The measure of the protective effect is considered the time to achieve a carbonyl extinction of approximately 0.30, at which time the comparative film is fragile. Light stabilizers used in the examples. 1. Complex polyester of formula 1. 0О 1 - C-CHjCHj-C-O-CHjCHt CHj CHj where and 7. 2. Complex polyester, as 1, where h 5. 3. Complex polyester of the formula, 0 О,. 1 - .schsng) 4-с-о-СНгСНг-ЬО- о 4CH j j where h 4. 4. Polyester of the formula OOSNLS, c- (CHi) eCO-CHiCHa-lV ® CHj СНз where about 5. 5. Polyester of the formula CH3 CHj C-YoVC-O-CHjCHj CH3 CH3 where it is 3.5. b. Complex polyester of the formula v / CH3 CH 2 O CgHb O and I II .. - C – C – C 0 – CH 2 CH г V V CH 2 CH 2 where h 6,5. 7. Compound polyether of the formula - O СФНэ ОСНз СНз t - - С С - С - ОннНСН2-т у о-АН9СН / Шз where .h is 3,5. 8. Complex polyester of the formula J1 CH) fi G V jc- (CHt) rC-o-ai # HrN CH CHj CH3 CH 3
    Where; h 4.
    9. A polyester of the formula CH3 CH 2 Hz vVNHCO-1 CHaUCY 3 CH 3
    where and 6.
    where n is 9.6.
    14. Complex polyester-amide of the formula de h 4,2. 10. Polyester of the formula CH3 CH2 | -0-5i-0-CH2CH2-K CH3 CH2 CH3 daH 5.4 11. Complex polyester of the formula CH3 CH3 -1 O-Si-0-CH2CHn-N (4L 3CH3 CH2 de .h 5.7 12. Polyester of the formula: nsnsnz CHz CHj de h 7 13. Polyamide of the formula O O O) oO (CHt) t Nli-C-C-1OT (CH 2) s-ll-C-CHj) -c4HjcrVcH, HjC W СНзHjCrSi CH, СНч СН. , Q CONH- jNCH 1 - /) to CH СН20С (СН2) + Jn СНз СНз 15. Polyamide of the formula Io 4-N (CHj) 6N-C- (CH,. D СНз СН, Л L JL1Jtl CHj.ri.CH , CHjriCHx g c3 cHjY nn where h is 9. 16. Polyamide, as 15, where H. 3. 17. Compound polyester of the formula, -sn "-sn, J1 I o cHjcHj ShzJn
    where and 9.
    18. Complex polyester formula
    CHj, CHjСН ,, CiHjO-.
    SNL CHj
    -CHr-CH-CH-CHrI Ml-C - with 44-o- (Vci
     tiHs
    J ... Jn cHi,
    where h is 12.5.
    19.- Polyester Formula
    3 CHj 0
    {r 8
    Mr.SOCHjCHj Shz Shz
    (sleep)
    he is 11314 10
    where h is 11.
    23. Polyurethane formula
    0 I
    I o "- Wi -NK-c -1-CI CHj-
    where and 18.
    24. Polyamine Formula
    SIS CHE
    HE
    - - KN-LuK-CH2-CH
    where P 12.
    25. Polyamine of the formula 2-8 8. Polyester of the formula CH3 CH5 Lx W 3 R 3 where and 16. 22. A complex polyester of the formula g (1 cn, xi, 4-o- (Xvn, very good N-cHCH cHCHr-i (o- s-s-s- | 1gSN SNSNg-1. SI} CHs SI SI)
    where and. 6
    20. Complex polyester formula
    HE
    where I 9.5.
    -4-1; -sng-sn he) -sng4
    5 L J-Itti
    SNS
    CH
    polyester, formula. Oh CHj Ch, v
    Ij
    -c cf-СНгСН-CHiI Jii CHj 27. Compound polyester of the formula Сш СН СЗ С О С hell On -I- o- (Sj-cHi-in-с- с-с -h СНз where h 9,. The protective effect of the proposed stabilizers is shown 1. Light-protective effect of polypropylene fibers 1000 parts by weight of unstabilized polypropylene powder (melting index 18 g / min, 2.16 kgf at) are transferred in a drum mixer from 1 May, h pentaerythritol-tetracys- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionate and 2.5 parts by weight of light protective agent (Table 2), and then extruded in an extruder at 220 C and guaranteed The resulting granulate pho 570/12 denier filament yarn in a laboratory apparatus for forming from a melt at a maximum temperature of 270 ° C and a speed of 300 m / min, after which it is pulled out and spun by a torsion machine. The stretch ratio is 1: 5 , 6, the torsion number is 15 m. A 120/12 denier filament is obtained in this way. The filament yarns are attached to white cardboard and irradiated in a weathering instrument (WRC 600). A measure of the protective effect is the irradiation time to creep 50 % loss of low strength. The research results are summarized in table 2. PRI m and p 3. The light shielding of polyethylene films obtained by extrusion, blown. 100 ma.ch. polyethylene low. density (melting index 0.1-0.3, at 2.16 kgf 190 is mixed for 2 min in a cooled intensive mixer of the firm Henshel e 0.15 wt. parts of compound 1 as a light shielding agent and, 0.03 May. 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -octadecylpropionate as an antioxidant extrudate in a single-screw extruder with a diameter of 35 mm and a length of 700 mm, and the temperature in the first stage is 190 ° C, and the next three to 200 ° C, cooled with water and the granulation is pelletized with an extruder having a diameter of 600 mm and a length of 1200 mm for extrusion and blown-through. The extruder has a die with annular, concentrically disposed outlet openings, the temperature of which is set to 200 C. The film pushed out in the form of a sleeve is blown at a ratio of 1: 1.8. The film receiving speed is 5 m / min. It is irradiated in a weather resistance apparatus (Weser 600), and periodically every 18 min is sprayed with water and irradiated for 102 min in a dry state. At regular intervals, the tensile strength of the irradiated film is measured. After 2400 hours, the elongation at rupture is 62% of the initial value. The counter film, obtained without a light-shielding agent, already after 610 hours of irradiation shows a decrease in elongation upon discharge to 50% of the initial value. PRI me R 4. Light shielding polyurethane film. 100 ma.ch. aromatic polyester polyurethane (Goodrich's Estane R 5707) is dissolved cold in 400 mash. dimethylformamide. Additives listed in Table 3 are added to this solution. Installed on a 500 micron film extractor, films on a glass plate are drawn and dried for 20 minutes at 120 ° C in a convection drying chamber. Films of approximately 60 microns are obtained. Samples are irradiated in a xenotest 450. In a separate test, samples are sprayed with water periodically every 28 minutes and 102 minutes irradiated in a dry form. At regular intervals, the films are tested for tensile strength. The stabilization measure is given in Table 3, the irradiation time to reduce the relative elongation at break to 50% of the initial value. PRI me R 5. Light shielding ABS copolymers. 1000 ma.ch. bulk polymerized acrylonitrile butadiene copolymer with 10% butadiene content is mixed with e 10 wt.h. Compound 1 as a protective agent, 2 ma.h. 2, b-di-tert-butyl-4-methylphenol as an antioxidant and 3 wt.h. Trisnonylphenyl-, phosphite as a stabilizer and processed in an atomomat for injection under pressure at 240 ° C into test rods according to DIN 53453 which are irradiated in xenotest 450 and then subjected to an identical test of DIN 53453 for damage, and beat with a hammer on the non-irradiated side. Test rods are not irradiated. The measure of the protective effect is the irradiation time until the loss of toughness to 20 KrC / CM. Example 6: Comparison of migration and extraction resistances of polymeric and low molecular weight light protective agents in polypropylene. 1000 ma.ch. un stabilized polypropylene powder melting index 18 g / 10 min; 1.16 kgf at 130 ° C) is mixed with 2 wt. 1,3,5-trimethyl-4,4,6-tris- (3,5-di-tert.-butyl-4-hydroxybenzene 1) -benzene and e 5 wt.h. one of the below light stabilizers and process at 200 ° C for 10 min in a plastograph Wrabender. The polymer stabilized in this way is compressed for 6 minutes at 260 C on a 0.5 mm thick plate and immediately. After that, they are cooled in cold water. Control samples of 2 x 4.5 cm in size are stamped from the plates, which on one side are tested for migration resistance at 120 C in a convection drying chamber, and on the other, they are subjected to aqueous extraction at 90 C. the light of the protective control means is determined at regular intervals by infrared spectral analysis. Table 5 shows the time after which the initial concentration of the light protective agent is reduced to half. The following are used as a light shielding agent: A. Polyester complex of the formula about SchNe O CH, CH2-0-C-C CHz CHj 212 (proposed compound 19). B. A compound of formula CH3. СНз / - п г / 1 THO- 2 СН7-Г С 4-СОО - /) КН 1 СНз СН, Pre 7. Comparison of the thermal-oxidative resistance to yellowing of the ABS-copolymer. 100 ma.ch. polymerized in the mass of acrylonitrile butadiene styrene polypinera (butadiene content 10%) is mixed with 1 mac.h. from the stabilizers on the roller machine indicated in table 6 into plates with a thickness of 22 mm, which are then hung in a convection drying chamber set at 80 ° C and through 500 hours set by yellowing of the yellowness index according to STMD No. 1925-70. The higher the yellowness index, the more yellowing it is. The stabilizers used are: A. A polyester compound of the formula. СНз СН, СНз СНз C, Hj 1 I (2) л1} с-со-ь СНз СНзСНз СНз CjHs where 1 9.5 (stabilizer 28), B. Composition of the formula СНз СНз гч-Iг Ulj v-nj «- NOSHU-CH2-C-COO-W4cjcHj) 3 JL (Example 3 of a known composition) B. Compound of the formula CTC, .c "C CHTcHsJ. (Example 5 of a known composition) EXAMPLE 8. Light-protective effect in polystyrene. 500 g of unstabilized polystyrene granulate with a melting index of 1.2 g / 10 min (at 200 s and a pressure of 5 kgf) are mixed with 2.5 g of the stabilizer (Table 7) in a 2-liter bottle for 25 minutes. This mixture is extruded in a single-screw extruder at 210 C (120 rpm) and at 200 C is pressed into 1 mm thick plates from which test samples 4 x 4 cm in size are cut and irradiated in the AL 600 device. At equal intervals of time Desirable yellowing by yellowness index of ASTM 1925-70. The measurement results in table 7 show the effect of the proposed compounds. The formula of the stabilizer is 28A SNS: ns sns-gbGG OCHjCHi gL kSNzSN –C CHZ) where P is 11.5. Shl SNZ SNZ. C - -f- J v «,, - -,. СНз СНз СНз Ш
    where P 9,5.
    Example 10. Comparison comparison in low density polyethylene,
    260 ma.ch. unstabilized poly-Y3 ethylene powder (Ackatene 15017 from JSJL + d, density 0.917) is plaitified for 3 min at 30 rpm. After this, the next 120 mars. Hours is added. polyethylene powder together with 1.9 mach. stabilized stabilizers and continue to plasticize for another 7 minutes. Then, the homogenized mass is pressed by direct pressing at 170 C into 0.5 mm thick plates, from which control samples of 8x4 cm are cut out and put for 4 days in an oven, then us-sanavA-CHU-LT
    where P 8,5.
    Table 10 shows the degree of fading of the known and proposed stabilizers.
    The degree of stabilizer fading is shown.
    Stabilizer formula 30
    About o - | W) -O l
    ABOUT
    where 1L 6.
    Stabilizer formula 32
      ™
    where 10.
    Formula stabilizer 33
    Example 11 Compatibility in low density polyethylene with a high concentration of stabilizers. PRI me R 9. Light-shielding effect of styrene-acrylonitrile-copolymer. . 500 g of unstabilized SAN granulate (containing 26% acrylonitrile and 74 styrene) with a melting index of 0.7 g / 10 min (at 200 ° C and a pressure of 5 kgf) are mixed with 2.5 g of stabilizers in a 2-liter bottle in for 25 minutes This mixture is extruded in a single-screw extruder at 210 ° C at 120 rpm and pressed into plates 1 mm thick, from which control samples 4x4 cm in size are cut out and irradiated in a WRC 600 gauge. Yellowness index is established at regular intervals by means of a yellowness index according to ASTM 1925-70. The measurement results shown in table 8, show the effect of the proposed compounds. The stabilizer formula is 29 Jn In 1511. Cooking puddles with a thickness of 0.5 mm and a size of 8x4 cm are prepared according to example 10, but with a stabilizer content of 2 wt.h., which is stabilizer 17, as well as a stabilizer of the formula O O -f 0 - () m-CHg CH- CH-CHi - "() - 0-C CHtCH, -c} n where 11.5. (stabilizer 31). Both samples after one year of storage did not show fading. Example 12. Light protection of polypropylene strips with a low concentration of stabilizers. 100 May ... h polypropylene powder (melting index 1.5 g / 10 min. 230 C, 2160 g load) is mixed in a drum mixer with 0.05 wt.h. Pentavitrite-tetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.05 wt.h. given in table 11 light protective agents and 0.05 wt.h Tris (2,4-di-tert-butylphenyl) phosphate is then granulated in an extruder at 200-220 ° C. The granules obtained are processed using a slit die extruder by means of an ordinary method into films that are cut into strips, which are then pulled out at elevated temperatures to six times the length. The titer of these hollows is 700-900, their width is mm, and the tensile strength is 5.5-6.5 g / denier. The strips were irradiated for 1200 hours at a 1200 xenotest, while at the same time setting a decrease in tensile strength. In a separate test in xenotest, 450 samples are sprayed with water periodically every 18 minutes and 102 minutes irradiated in a dry form. At regular intervals, the films are tested for tensile strength. The measure of stabilization is the time of irradiation given in Table 3 to reduce the relative elongation at break to 50% of the initial value. In addition, the color change under dry irradiation is established by measuring the transmittance at 420 nm. Table 12 shows the irradiation time to 15% loss of light transmission. to Example 13. Polyamide-6 fiber. 100. ma.ch. polyamide-6 granulate containing 0.28% titanium oxide and 5.2 ppm. manganese, dried under vacuum (50 mm of mercury) for 24 hours at 90 ° C, then stirred for 2 minutes in an intensive mixer with 0.5 wt.h. given in table 13 stabilizer. This mixture is spun in an extruder at 17 fibers of just 170 denier and stretched to a ratio of 1: 3.8. These tension-free fibers are wound onto cards and irradiated at 1200 xenotes. The tensile strength is checked first and after 2000 hours. The results in Table 13 show the effect of the proposed stabilizers. Table 1
    17
    0.5
    four
    0.25
    five
    0.25
    b
    0.25
    7
    0.25
    0.25
    eight
    9
    0.25
    0.25
    10 11 12 13 14 15 18 19 20 21
    0.25
    0.25
    0.25
    0.25
    0.25
    0.25
    0.25
    0.25
    0.25
    0.25 22
    0.25 23 24 25 26
    0.25
    0.25
    0.25
    one
    About control
    1131472
    18 Continuation of table 1
    2200 8180 5060 6970 6920, 5730 8600 8600 3200
    . 1210 1950
     /
    3060
    . one
    4700 2360 1930 2030
    4700 2120 4230 4760
    690
    550 400 91. Table Light-shielding Duration of exposure to 50% (compound) breaking strength, h. 22000 51550 262150 272200 Wes ee.to, protective. agents525 Light protective agent Without light protective agent С 1% of compound 1; Light-shielding Time, h by means — which end of light shielding due to water. decreases A3000 B1800 Stabilized
    A B C
    23.4 57.3 34.7 131472 Table 3 g Light-shielding Irradiation time, h means up to 50% reduction in relative elongation, ® dry 1 when wet, light-shielding agent 210 180 С 0.5 wt.h. Compounds 1-1090; 90 - Table4 Irradiation time, hours up to residual viscosity up to 20 kgf / cm "cm 300 450 tons of face 5 time out, h after expiration of which concentration is average. extraction light shielding due to migration at 90 ° C with a decrease of 50% to 50% 3000. 110 T a b i c a 6. opus yellow index, after 500 h at 80 C Stabilizer Without stabilizer 1 28 A,, -, „,, 11,, 11 and, g II J | that 11. L DIILSHSH, LL Stabilizer Without stabilizer 1 28 29,.-.- .- .. 1,1 - .., ..., Table 9 g: Stabilizer Enlightenment I - -30. Weak 32 no 33 weak; Light protective (stationary) Without stabilizer 1. 17 Table 7 Irradiation time, h 100020003000 g 11,128,232.9 5,712,119.9 9,919,427.9 / w - m c L1 | | tzh TsZh11I tsh 1 And | T 1blt8 Irradiation time, h 1000 I 3000 13.835.8 5.313.0 5.414.70, 227.9. “.. --.- - - Tables and jp Stabilizer Enlightenment. .. Suggest a H3BecTHHu | 2j example: 1 Strong 3 Strong 5A very strong tablePrecision on erosion after 1200 hours of baseline. % 30 100 100
    权利要求:
    Claims (1)
    [1]
    POLYMER COMPOSITION: Containing a polymer selected from a group including a polyolefin, a homo or copolymer of styrene, a polyester-based polyurethane and polycaproamide, and a stabilizer, characterized in that it contains a compound selected from the group as a stabilizer to stabilize the composition, comprising a polyester of the general formula
    C (CH3) s - C4H9 — C — CH ^ - ^ O ^ —OH or
    C (CH 3 ) s
    -sng-sn (ssz) -sn2-s (ssz) 2 -,
    CHz CHz in -sn g sn g -and ^ ~ ->
    SNGSNZ
    SU, m 1131472
    WHERE A - f CH r b, - <^ - gC (CrH5) gCH
    SNZ
    СНз СН 3 or • С (С4Н9) 2 -, - С, Н (СН g СБН5) - ·,
    N-CHtCH "-;
    -sn g sn g- and
    CHs'CHs CHs sn 3 where tn. = 2-8 and n = 3,5-16,5 general formula wherein h = 9,5, of the general formula where, h = 7 and g of general formula CH oh oh DOP,
    T ° L ^^ '^ ’SI-cng-tO'O-Cr-E- with X
    CH3 sn 3 cHj with Hj Jn where Е-ССДд) ^, -CCCaHj). * -, -01 ((¾¾ Н 5 ) - or-С (С 4 Н „), -, = 2-8 and h = 6 -12.5 in the following ratio of components, ma.ya .:
    Polymer 100
    Stabilizer .0.05-2
    类似技术:
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    US2998405A|1961-08-29|Stabilized polyolefin compositions
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    SU508217A3|1976-03-25|Polyolefin Composition
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    同族专利:
    公开号 | 公开日
    DE2760429C2|1990-05-17|
    US4260689A|1981-04-07|
    JPS52141883A|1977-11-26|
    DE2719131C2|1989-08-24|
    MY8400250A|1984-12-31|
    CA1126446A|1982-06-22|
    GB1568839A|1980-06-04|
    NL190873B|1994-05-02|
    CH626109A5|1981-10-30|
    NL7705092A|1977-11-15|
    US4299926A|1981-11-10|
    AU515669B2|1981-04-16|
    US4233410A|1980-11-11|
    NL190873C|1994-10-03|
    HK42283A|1983-10-21|
    SG28983G|1984-04-19|
    US4260691A|1981-04-07|
    DE2719131A1|1977-12-01|
    US4233412A|1980-11-11|
    FR2351144A1|1977-12-09|
    AU2502877A|1978-11-16|
    FR2351144B1|1979-07-13|
    BE854489A|1977-11-14|
    US4232131A|1980-11-04|
    JPS61118437A|1986-06-05|
    JPH0223580B2|1990-05-24|
    JPS6335658B2|1988-07-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3383365A|1964-09-09|1968-05-14|Monsanto Co|Polyurethane elastomers derived from dipiperidyl chain extenders|
    US3640928A|1968-06-12|1972-02-08|Sankyo Co|Stabilization of synthetic polymers|
    US3705126A|1969-06-20|1972-12-05|Sankyo Co|Stabilization of synthetic polymers|
    BE755461A|1969-08-29|1971-03-01|Bayer Ag|POLYESTERS CONTAINING TERTIARY NITROGEN ATOMS|
    US3684765A|1970-01-08|1972-08-15|Sankyo Co|Stabilization of synthetic polymers|
    NL154241C|1971-01-29|1900-01-01|
    US3941744A|1971-06-05|1976-03-02|Sankyo Company Limited|Piperidine derivatives and their use as stabilizers|
    BE785742A|1971-07-02|1973-01-02|Sankyo Co|PIPERIDINE-SPIRO-HYDANTOINS AND THEIR USE AS STABILIZERS|
    US3859293A|1971-11-13|1975-01-07|Sankyo Co|N-substituted spiro piperidine derivatives|
    US4021432A|1971-11-30|1977-05-03|Ciba-Geigy Corporation|Piperidine derivatives|
    US3790525A|1972-01-21|1974-02-05|Sankyo Co|4-piperidone ketal derivatives,their preparation and their use as stabilizers|
    JPS554133B2|1972-07-27|1980-01-29|
    GB1398414A|1972-07-28|1975-06-18|Ciba Geigy Ag|Piperidine derivatives|
    GB1398412A|1972-07-28|1975-06-18|Ciba Geigy Ag|Piperidine derivatives|
    GB1398413A|1972-07-28|1975-06-18|Ciba Geigy Ag|Piperidine derivatives|
    US3974127A|1973-09-17|1976-08-10|E. I. Du Pont De Nemours And Company|Alkylene oxide condensates of tetramethylpiperidine alcohols or glycols|
    US3901853A|1973-09-17|1975-08-26|Du Pont|Acid-dyeable fibers of polyester modified with a tetramethylpiperidine compound having two ester-forming groups|
    US4001190A|1973-09-17|1977-01-04|E. I. Du Pont De Nemours And Company|Acid-dyeable fibers of polyester modified with tetramethylpiperidine polyether glycols|
    AU6038573A|1972-09-20|1975-03-20|Du Pont|Improvement in dyeing polyester fibers|
    JPS557861B2|1972-10-04|1980-02-28|
    NL179392C|1975-03-21|1986-09-01|Montefibre Spa|A METHOD FOR PREPARING STABILIZED POLYMERIC COMPOSITIONS AND A METHOD FOR PREPARING POLYAMINS SUITABLE AS A STABILIZER, AND MANUFACTURED THEREFOR.|
    IT1061551B|1975-11-18|1983-04-30|Chimosa Chimica Organica Spa|POLYUREIC COMPOSITES USED FOR THE STABILIZATION OF SYNTHETIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION|
    CH623066A5|1976-05-11|1981-05-15|Ciba Geigy Ag|
    DE2642461A1|1976-09-21|1978-03-30|Bayer Ag|PERMANENTLY STABILIZED POLYMERS|
    DE2642386A1|1976-09-21|1978-03-23|Bayer Ag|PERMANENTLY STABILIZED POLYURETHANES|US4243792A|1977-05-11|1981-01-06|General Motors Corporation|Moisture curing polyurethane topcoat paint with improved gloss stability|
    JPS6332782B2|1977-08-08|1988-07-01|Sankyo Kk|
    US4256627A|1977-11-08|1981-03-17|Ciba-Geigy Corporation|Novel light stabilizers for plastics|
    US4279720A|1978-07-13|1981-07-21|Ciba-Geigy Corporation|Photocurable composition|
    EP0007468B1|1978-07-13|1982-04-07|Ciba-Geigy Ag|Compositions photodurcissables|
    EP0007736B1|1978-07-25|1983-10-12|Imperial Chemical Industries Plc|Polyolefin articles sterilisable by gamma-irradiation|
    DE2839711A1|1978-09-13|1980-03-27|Hoechst Ag|NEW POLYALKYLPIPERIDINE POLYMERISATES, THEIR PRODUCTION AND USE|
    US4311820A|1979-02-14|1982-01-19|Ciba-Geigy Corporation|Homopolymers and copolymers of vinyl ethers of polyalkylpiperidinols and their use as stabilizers for plastics|
    EP0022079B1|1979-06-21|1984-01-18|Ciba-Geigy Ag|Polyalkylpiperidyl ureas, their application as stabilizers and polymers thus stabilized|
    IT1193839B|1979-11-06|1988-08-24|Montedison Spa|N, N-DI-ALCANOL-AMINE POLYESTERS WITH MALONIC DI-ACIDS AND THEIR USE AS POLYMER STABILIZERS|
    US4348524A|1980-03-28|1982-09-07|Ciba-Geigy Corporation|Amide derivatives of polyalkylpiperidines|
    US4265805A|1980-04-01|1981-05-05|American Cyanamid Company|Polymeric light stabilizers containing tetralkyl piperidine moieties|
    DE3022896A1|1980-06-19|1981-12-24|Hoechst Ag, 6000 Frankfurt|POLYTRIAZINYLAMINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS STABILIZERS FOR SYNTHETIC POLYMERS|
    IT1151035B|1980-07-31|1986-12-17|Chimosa Chimica Organica Spa|PIPERIDYL-DERIVATIVES OF TRIAZINIC COPOLYMERS, PROCESSES FOR THEIR PREPARATION AND STABILIZED COMPOSITIONS THAT INCLUDE THEM|
    AU7424681A|1980-09-10|1982-03-18|B.F. Goodrich Company, The|Piperidine derivatives as u.v. stabilisers|
    DE3111209A1|1981-03-21|1982-09-30|Hoechst Ag, 6000 Frankfurt|HIGH MOLECULAR PIPERIDING GROUP-CONTAINING ESTERS AND URETHANES, METHOD FOR THE PRODUCTION THEREOF, THEIR USE AS STABILIZERS FOR POLYMERS AND POLYMERS CONTAINING THESE COMPOUNDS|
    JPS6354022B2|1981-04-23|1988-10-26|Adeka Argus Chemical Co Ltd|
    DE3118962A1|1981-05-13|1982-12-09|Hoechst Ag, 6000 Frankfurt|PHIPHAZENE SUBSTITUTED BY PIPERIDYL GROUPS, METHODS FOR THE PRODUCTION THEREOF, THEIR USE AS STABILIZERS AND THE POLYMER MATERIALS STABILIZED WITH THEM|
    US4331586A|1981-07-20|1982-05-25|American Cyanamid Company|Novel light stabilizers for polymers|
    US4444928A|1981-08-14|1984-04-24|Ciba-Geigy Corporation|Polymeric malonic acid derivatives|
    US4370430A|1981-08-31|1983-01-25|American Cyanamid Company|Hindered amine light stabilizers for polymers|
    JPS631981B2|1981-09-19|1988-01-14|Mitsubishi Yuka Kk|
    EP0080431B1|1981-10-16|1986-09-24|Ciba-Geigy Ag|Synergistic mixture of low and high molecular weight polyalkyl piperidines|
    US4480092A|1982-02-19|1984-10-30|The B. F. Goodrich Company|Alkylated polyalkylenepolyamines, substituted oxo-piperazinyl-triazines|
    US4507415A|1982-03-27|1985-03-26|Terumo Kabushiki Kaisha|Medical articles|
    JPH0243770B2|1982-04-15|1990-10-01|Mitsubishi Petrochemical Co|
    US4520171A|1982-05-05|1985-05-28|Hercules Incorporated|Polymeric hindered amines|
    JPS6116775B2|1982-11-01|1986-05-02|Adeka Argus Chemical Co Ltd|
    US4439565A|1982-11-10|1984-03-27|Ciba-Geigy Corporation|Oligomeric esteramides containing pendant hindered amine groups|
    US4556714A|1983-01-24|1985-12-03|Ciba-Geigy Corporation|N--carbamates of polyols|
    DE3468866D1|1983-03-21|1988-02-25|Ciba Geigy Ag|Oligo esters containing polyalkyl piperidine groups|
    IT1164214B|1983-05-09|1987-04-08|Chimosa Chimica Organica Spa|POLYMERIC COMPOUNDS CONTAINING PIPERIDINIC RADICALS, PROCESS FOR THEIR PREPARATION AND USE AS STABILIZERS FOR SYNTHETIC POLYMERS|
    US4507463A|1983-05-11|1985-03-26|Ciba-Geigy Corporation|Process for producing polyesters from aliphatic dicarboxylic acids and polyalkylpiperidyldiols|
    US4535145A|1983-07-08|1985-08-13|Ciba-Geigy Corporation|Process for the preparation of polyesters from aliphatic dicarboxylic acids and polyalkylpiperidyl diols|
    IT1163815B|1983-07-19|1987-04-08|Chimosa Chimica Organica Spa|POLYMERIC COMPOUNDS CONTAINING PIPERIDINIC RADICALS PROCESS FOR THEIR PREPARATION AND USE AS STABILIZERS FOR SYNTHETIC POLYMERS|
    US4504612A|1983-09-26|1985-03-12|E. I. Du Pont De Nemours And Company|Polyester antifume additive for spandex fiber|
    US4696959A|1983-09-26|1987-09-29|Ppg Industries, Inc.|Modified piperidines as ultraviolet light stabilizers|
    EP0160642B1|1983-10-13|1989-02-08|E.I. Du Pont De Nemours And Company|Polymeric light stabilizers containing polyalkylpiperidine groups|
    AU567702B2|1983-10-13|1987-12-03|Ford Motor Company Of Canada Limited|Polymeric light stabilizers containing polyalkylpiperidine group.|
    JPH0642083B2|1984-08-27|1994-06-01|住友化学工業株式会社|Toner for electrostatic image development|
    US4944740A|1984-09-18|1990-07-31|Medtronic Versaflex, Inc.|Outer exchange catheter system|
    US4960593A|1985-01-30|1990-10-02|Hilmont Incorporated|Process for preparing thermally stable olefinic polymers|
    JPH0531583B2|1985-08-28|1993-05-12|Mitsubishi Petrochemical Co|
    IT1212123B|1986-02-21|1989-11-08|Ciba Geigy Spa|NEW POLYMERIC COMPOUNDS CONTAINING PIPERIDINE GROUPS, USABLE AS STABILIZERS FOR SYNTHETIC POLYMERS.|
    US4863981A|1986-06-30|1989-09-05|Ciba-Geigy Corporation|Synergistic mixture of stabilizers|
    DE3731843C2|1986-09-25|2002-03-21|Ciba Sc Holding Ag|Process for stabilizing polyethylene films|
    EP0290386B1|1987-05-05|1992-06-10|Ciba-Geigy Ag|Stabilization of organic polymers against light degradation|
    US4751073A|1987-06-03|1988-06-14|Olin Corporation|Selected 2,2,6,6-tetraalkyl-4-piperidinyl derivatives and their use as light stabilizers|
    US5210119A|1987-10-16|1993-05-11|General Electric Company|Polymer mixture comprising polyphenylene ether, sterically hindered amine and epoxy compound and articles manufactured therefrom|
    NL8702473A|1987-10-16|1989-05-16|Gen Electric|POLYMER MIXTURE WITH POLYPHENYLENE ETHER, STERICALLY Hindered AMINE AND EPOXY COMPOUND AND ARTICLES THEREFOR.|
    US4882412A|1987-11-30|1989-11-21|Eastman Kodak Company|Polyester polymer containing the residue of the UV absorbing benzopyran compound and shaped articles produced therefrom|
    US4892923A|1988-02-22|1990-01-09|Eastman Kodak Company|Polyester compositions containing the residue of a naphthopyran compound and shaped articles produced therefrom|
    US4859759A|1988-04-14|1989-08-22|Kimberly-Clark Corporation|Siloxane containing benzotriazolyl/tetraalkylpiperidyl substituent|
    US4927898A|1988-09-06|1990-05-22|Union Carbide Chemicals And Plastics Company Inc.|Polysiloxanes with sterically hindered heterocyclic moiety|
    FR2642764B1|1989-02-03|1993-05-28|Rhone Poulenc Chimie|NOVEL PIPERIDINYL FUNCTIONAL COMPOUNDS AND THEIR APPLICATION IN THE PHOTOSTABILIZATION OF POLYMERS|
    US5096948A|1989-07-03|1992-03-17|Sankyo Company, Limited|Resistant resin compositions|
    JP3041823B2|1989-09-09|2000-05-15|クラリアントファイナンス（ビーブイアイ）リミティド|Synthetic polyamides and their salts|
    DE3932912A1|1989-10-03|1991-04-11|Sandoz Ag|Synthetic polyamide for plastics, inks and lacquers|
    US5132387A|1991-01-07|1992-07-21|Elf Atochem North America, Inc.|Hindered amine light stabilizer hydrazides for stabilizing polyurethane, polyurea and polyurethane-polyurea polymers|
    US5149723A|1991-03-22|1992-09-22|E. I. Du Pont De Nemours And Company|Stabilized polyacetal compositions containing a mixture of hals having tertiary functionality|
    JP3082333B2|1991-09-03|2000-08-28|住友化学工業株式会社|Stabilized polyolefin composition|
    US5169949A|1991-09-30|1992-12-08|Himont Incorporated|Monomeric hindered amine esters of monocarboxylic resin acid having 20 carbon atoms|
    US5453295A|1992-01-15|1995-09-26|Morton International, Inc.|Method for preventing filiform corrosion of aluminum wheels by powder coating with a thermosetting resin|
    TW252991B|1992-12-04|1995-08-01|Ciba Geigy|
    US5380591A|1992-12-30|1995-01-10|Union Carbide Chemicals & Plastics Technology Corporation|Telephone cables|
    CA2131047A1|1993-09-01|1995-03-02|Takashi Sanada|Thermoplastic resin composition|
    DE4403084A1|1994-02-02|1995-08-03|Basf Ag|Condensation and addition polymers with N, N'-bridged bis-tetramethylpiperidinyloxy groupings|
    TW350859B|1994-04-13|1999-01-21|Ciba Sc Holding Ag|HALS phosphonites as stabilizers|
    TW297822B|1994-04-13|1997-02-11|Ciba Geigy Ag|
    TW317568B|1994-04-13|1997-10-11|Ciba Sc Holding Ag|
    US5453322A|1994-06-03|1995-09-26|Union Carbide Chemicals & Plastics Technology Corporation|Telephone cables|
    EP0709426B2|1994-10-28|2005-01-05|Ciba SC Holding AG|Synergistic stabiliser mixture|
    TW357174B|1995-01-23|1999-05-01|Ciba Sc Holding Ag|Synergistic stabilizer mixture|
    TW401437B|1995-02-10|2000-08-11|Ciba Sc Holding Ag|Synergistic stabilizer mixture|
    TW358820B|1995-04-11|1999-05-21|Ciba Sc Holding Ag|Synergistic stabilizer mixture|
    DE19516701A1|1995-05-10|1996-11-14|Hoechst Ag|Plastic with reduced sulfur absorption rate|
    IT1275584B1|1995-07-21|1997-08-06|3V Sigma Spa|COMPOSITIONS FOR THE STABILIZATION OF SYNTHETIC POLYMERS|
    DE19631993A1|1996-08-08|1998-02-12|Huels Chemische Werke Ag|New moisture-curing PUR hot melt adhesives|
    JP3658880B2|1996-08-26|2005-06-08|三井化学株式会社|Polyolefin composition|
    DE19820157B4|1997-05-13|2010-04-08|Clariant ProdukteGmbh|New compounds based on polyalkyl-1-oxa-diazaspirodecane compounds|
    AR018063A1|1998-02-13|2001-10-31|Basf Se|POLYAMIDE INHERENTLY STABILIZED AGAINST LIGHT AND HEAT AND METHOD FOR OBTAINING IT.|
    US6096826A|1998-07-21|2000-08-01|Air Products And Chemicals, Inc.|Piperidone functionalized poly|
    US6214995B1|1998-12-22|2001-04-10|Richard F. Stockel|Reactive hindered amine light stabilizers|
    US6946517B2|1999-08-17|2005-09-20|Ciba Specialty Chemicals Corporation|Stabilizer mixtures|
    JP5498638B2|2000-05-31|2014-05-21|チバホールディングインコーポレーテッド|Stabilizer mixture|
    US6727300B2|2000-11-03|2004-04-27|Cytec Technology Corp.|Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds|
    US6492521B2|2000-11-03|2002-12-10|Cytec Technology Corp.|Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same|
    US6545156B1|2000-11-03|2003-04-08|Cytec Technology Corp.|Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same|
    US6414155B1|2000-11-03|2002-07-02|Cytec Technology Corp.|Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same|
    US6620208B2|2001-03-30|2003-09-16|Honeywell International Inc.|Wetfast polyamide fiber with high amino end group content|
    US6761974B1|2001-05-04|2004-07-13|Seagate Technology Llc|Polymeric lubricants with improved stability and thin film recording media comprising same|
    US20040156933A1|2001-05-17|2004-08-12|Mcnamara John James|Polymer additives with improved permanence and surface affinity|
    JP2004530758A|2001-06-14|2004-10-07|ビー・エイ・エス・エフ、コーポレーション|Light-stabilized polymer, method for producing the same, method for producing thermoformable product using the polymer, and fiber obtained by the method|
    US20030236325A1|2002-05-30|2003-12-25|Michela Bonora|Agricultural articles|
    JP2005528497A|2002-05-30|2005-09-22|チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド|Stabilized article|
    US7861881B2|2004-10-28|2011-01-04|General Mills Cereals, Llc.|Removable overcap for microwaveable packaged good article|
    CA2524951A1|2004-10-28|2006-04-28|General Mills, Inc.|Microwaveable packaged good article overcap|
    CN101160348B|2005-04-18|2010-12-08|柯尼卡美能达精密光学株式会社|Cellulose ester film, manufacturing method thereof, optical film, polarizing plate and liquid crystal display|
    ITMI20052067A1|2005-10-28|2007-04-29|3V Sigma Spa|COMPOSITION FOR THE STABILIZATION OF SYNTHETIC POLYMERS|
    CN101374902B|2005-12-14|2011-05-04|住友化学株式会社|Polyolefin resin composition, molded product thereof and preparation of polyolefin resin composition|
    WO2009060043A2|2007-11-06|2009-05-14|Dsm Ip Assets Bv|Process for producing high molecular weight polyethylene|
    ITMI20080739A1|2008-04-23|2009-10-24|3V Sigma Spa|STERICALLY PREVENTED OLIGOMERIC STAKES AND THEIR USE AS STABILIZERS FOR POLYMERS|
    ITMI20080747A1|2008-04-24|2009-10-25|3V Sigma Spa|MIXTURES OF STERICALLY PREVENTED AMINES FOR THE STABILIZATION OF POLYMERS|
    US20120145236A1|2009-08-18|2012-06-14|Basf Se|Uv-stabilized photovoltaic module|
    IT1399477B1|2010-03-15|2013-04-19|3V Sigma Spa|MIXTURES OF STERICALLY PREVENTED AMINES FOR THE STABILIZATION OF POLYMERS|
    ITMI20110802A1|2011-05-10|2012-11-11|3V Sigma Spa|MIXTURES OF STERICALLY PREVENTED AMINES FOR THE STABILIZATION OF POLYMERS|
    KR101742845B1|2013-09-30|2017-06-01|주식회사 엘지화학|Optical film exhibiting excellent blocking property for ultraviolet rays and polarizing plate comprising the same|
    SA116370295B1|2015-02-20|2016-12-06|باسف اس اى|Light stabilized polyolefin films, tapes and monofilaments|
    IT201700073726A1|2017-06-30|2018-12-30|3V Sigma Spa|IMPEDITE POLYMERIC AMINS|
    IT201700078234A1|2017-07-11|2019-01-11|3V Sigma Spa|IMPEDINE MINES|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH589076A|CH626109A5|1976-05-11|1976-05-11|
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