• 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:
    The use of certain prepolymers of 4,4'-methyienebis-(phenyl isocyanate), in place of the latter diisocyanate itself in the preparation of polyurethane-polyureas using aromatic diamine extenders, has a number of advantages par- ticuiariy when the compositions are prepared by reaction injection molding techniques using two streams of reactants. The principal advantages are (i) a useful increase in gel time and (ii) a ratio of amounts of the two reactant streams which more nearly approaches 1:1. This latter factor not only improves the efficiency of mixing of the components in the mixing head but, together with the longer gel time, significantly increases the output of mixed reactants per unit of time. The prepolymers of 4,4'- methyienebis(phenyi isocyanate) employed to achieve the above results are those derived from polyoxy-ethylene polyoxypropylene polyether diols and triols (MW = 1000-10.000), polytetramethylene glycols (MW = 600-5.000) and polyester diols and triols (MW = 500-8.000).
    公开号:SU1512485A3
    申请号:SU823496035
    申请日:1982-09-16
    公开日:1989-09-30
    发明作者:Харольд Ювен Джеймс；Рой Макклеллан Томас；Макмиллин Майкл；Логан Муррай Пат
    申请人:Дзе Дау Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:


    C / 1
    The invention relates to the synthesis of polyurethane with urea groups and can be used in the industrial production of molded products through the prepolymer production stage.
      151 The purpose of the invention is to increase the gel time while maintaining the properties of polyurethane ureas.
    The essence of the method is as follows.
    Two streams of precursors are used, which are introduced and mixed by a high pressure collision. One of these streams is a prepolymer with terminal isocyanate groups (stream A), the other is a mixture of polyol and diamine together with a catalyst and other target additives (stream B).
    Both streams are mixed together in such proportions that the ratio of isocyanate equivalents in stream A and sums of equivalents of groups containing active hydrogen in the stream is in the range of 0.8: 1-1.3: 1, preferably 0.4: 1 -2.5: 1.
    The proportions in which the aromatic diamine and polyol can be applied in stream B can vary widely, provided that the ratio in which stream A is mixed with stream B is such that the total ratio of groups with active hydrogen atom is C. stream B is in the range of 0.8-1.3 equivalents per equivalent of polyisocyanate in stream A.
    The preferred proportion of diamine to polyol in stream B is such that in the final reaction mixture the ratio of equivalents of aromatic diamine per equivalent of poly isocyanate is in the range of 0.7: 1-0.9: 1.
    Catalysts such as salts of organic and inorganic acids, organometallic derivatives of bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium , molybdenum, vanadium, copper, manganese, zirconium, as well as phosphine and tertiary organic amines. From olovoor- ganic catalysts such as octoate and stannous oleate, may be used dnbuti- lolovdiatsetat, dibutilolovodioktoa dibutyltin dilaurate, dibutyltin leat, dibutshtolovomerkaptopropionat dibutilolovododetsilmerkaptid, dibu5
    five
    g
    five
    0
    0
    50
    five
    Tyl-tin bis (isooctylthioglycol), and as an amine catalyst - triethylamine, triethylenediamine, N, N, N, N-tetram-ethylethylenediamine, N, N, N, N-tetraethylethylenediamine, N-methyl morpholip, N-ethyl morpholine , N, N, N, N-tetramethylguandin, N, N, N, N -tetramethyl-1,3-butan-diamine, N, N-dimethyl ethanolamine, N, H-diztil-ethanolamine, N, N-dimethylcyclohexylamine and mixtures of these compounds in any combination.
    The preferred catalyst is dibutyl tin.
    The catalyst is introduced in an amount of 0.01-5.00% of the total mass of the reaction mixture.
    As a prepolymer, the reaction product of 4,4-methylene-bisphenyl isocyanate with a compound selected from the group consisting of polyethermethylene glycol 1000-6500 polyethermethylene glycol mol.m. 650-2900, complex polyester mol.m. 500-5600, functionality from 2 to 3 with the ratio of NCO / OH- groups equal to 1: 0.05-0.50, as a solution in carbodiimide or in the reaction product of 4,2-methyl-bis-phenyl lysocyanate with 0 54-0.20 eq. dipropylene glycol and mixtures thereof.
    The method is carried out as follows.
    Example 1. Preparation of prepolymer.
    K 52.8 mach. (0.42 eq.) Of 4,4-methylene-bis- (phenyl isocyanate) (4,4-MDI) with stirring in a stream of nitrogen at 43-49 ° C, 5.87 wt.% HH (0.082 equiv.) Mixture of parts by weight of dipropylene glycol (DPG) and tripropylene glycol (TPG).
    To the mixture was added 31.33 mas. (0.018 equiv.) Polyoxyethylenopolyoxypropylene diol (Polyol SF-4005, mol.m. 3500). After stirring, raise the temperature of the mixture to 79-85 ° C and incubate with stirring under a nitrogen atmosphere for 2 hours.
    At the end of this time, an aliquot portion of this reaction mixture is taken and the content of the isocyanate equivalent (equal to 281.8) is determined in it. Then the reaction mixture is cooled to 60 ° C and 10 mas. Added at stirring. 4,4-MDI, in which part of the isocyanate is converted
    51
    ; In carbodiimide. Ieocyanate equivalent, 143. Stir for another 30 minutes after the end of the addition, then; let the mixture cool until. The prepolymer obtained in this way has an isocyanate equivalent of 252 and a viscosity at 1825 CC (Forpolymer A).
    ; In a similar way, a series of prepolymers is prepared using the components and proportions presented in Table 1. Example 2: A series of samples (1–9, Table 3) of polyurethane is obtained by mixing prepolymer A (stream A) and stream B .
    Stream B is obtained by mixing the following components, parts by weight: Polyoxypropylene glycol, blocked with ethylene oxide, grafted with 20% polyacrylonitrile, mol.m. 600 (D-440) 50,16 A mixture of 1-methyl-3,5-diethyl-2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diaminobenzene (80:20, respectively) (DETDA) 11.03 Dimethyl tin-alcohol TJ (UL-28) 0.05
    All 9 samples (1-9, Table 2) were prepared using different ratios of flows A and B, listed in Table 2 as an index.
    Stream A before mixing is preheated to 38 ° C, and stream B to 54 ° C.
    A mold of size 60.80x96, 52x 0.31 cm is used to mold the samples.
     about
    Before loading the form is heated to 60 ° C. The removal from the mold is carried out 1 minute after the end of the cycle and is cast under pressure in all cases, and each sample is cured for 1 hour before physical testing. I -.
    about
    Table 2 shows for each sample the ratios of equivalents of isrciate groups in stream A to equivalents of groups with an active hydrogen atom in stream B. The gel time is
    not 3.5 seconds.
    124856
    Primerz (control). Get 7 samples (10-16, table 3) according to the method described in example 2. with the Composition of flow A, ma.ch .:
    4,4-MDI 346
    TPG IG blend)
    ; - DOG39
    The composition of the stream, MA.h .: 10 SF-400515.05
    D-44048.05
    DETDA10.57
    UL-280,073
    The ratio of the flows A and B used in the manufacture of samples 10–16 is indicated in Table 3.
    The gel time is 2.4 s. PRI me R 4. Prepare 8 samples (17-24, Table 4) using flow A 20 and the procedure of Example 2, but flow B of the next sample, mac: D-44058,170
    DETDA8,720
    UL-280,058
    25 The ratio of flows A and B is shown in Table 4.
    The gelation time is 4.3 s. PRI me R 5. Prepared 8 samples (25-32, Table 5), using the same 3Q flow A and the procedure as in Example 2, but the composition of flow B is the following, mac.h .:
    D-440 - 39.90 DETDA13.96
    UL-280,04
    35
    Samples are prepared with the ratio of flows A and B indicated in Table 5, as an index.
    Gelation time
    2.7 e.
    PRI me R 6. Prepare 10 samples (33-42, Table 6) according to the procedure of Example 2, but the composition of flow B is the following, mac.ch .:
    Polyoxyethylene polyoxchfopylene
    Triol mol.m. 6500
    (SF-6503) 39.90
    DEDTA13,96
    UL-280,04
    The ratio of flows A and B (index) is shown in Table 6.
    Gel time 2.9 s.
    PRI me R 7. Prepare 7 samples (43-49, Table 7) according to the procedure
    example 2, but the flow In use the following composition, ma.ch .:
    D-440100
    4,4-mets 1512 85
    bis- (2,6-diisopropaniline) O-TOSHA) 66
    The ratio of flows A and B (in- t-deck) is shown in Table 7.
    Example A molded article was prepared according to the procedure of Example 2, but the following flow was used B
    composition, ma.ch .:
    Polyoxypropylene triol,
    blocked
    ethylene oxide mol.m. 750015
    (Voranol 5148) 100
    DETDA 35
    UL-280,2
    Streams A and B are mixed in a weight ratio of 0.9: 1.0, which corresponds to a 20-t index of 1.1.
    The averaged properties of solidified molded products (out of six values):
    Density 25
    g / cm3.07
    Hardness
    Shore D 59.00
    Elastic modulus at ras-30
    t,
    kg / cm:
    at 100% 172.3 200%. 237.3 300% 300.5 35
    Strength limit at
    stretching ,,
    kg / cm
    Elongation,% 290.0 40
    Break With
    matrices 691, 0
    Elastic modulus ,
    kg / cm at 45
    -29 ° С5130
    24 ° C. 3234
    - 70 ° С 2060
    The gel time is 3.2 s. 50 PRI me R 9. Six samples were prepared (50-55, Table 8) according to the procedure of Example 2, but 36.72 parts by weight were used as prepolymer A (stream A). 4,4-MDI, from 55 53.28 ma.ch. polyoxypropylene polyethyethylene polyol mol.m. 3500, and as a stream B the following composition, mac.h.:.
    t
    0
    five
    20
    25
    thirty
    35
    40
    45
    50 55
    eight
    D-440 48.91
    DATDA10.76
    Dare DPG and TPG
    in relation to
    1: 1 .2.86
    UL-280,06
    Streams A and B are mixed in the weight ratio indicated in Table 8. (index).
    The gel time for the used reaction mixture with an index of 1 is 2.6 seconds.
    PRI me R 10 (control). A series of samples is prepared (56-61, Table 9) according to the method of the example. 2
    But stream A is a polyisocyanate mixture obtained by mixing 4,4-MDI with the 4,4-MDI liquid form used in Example 1, at a weight ratio of 20.44: 4.19.
    As the flow In use the following composition, ma.ch .:
    D-440 .47.49
    SF-400514.86
    DATDA10.45
    Diztilenglikol1, 39
    . Tripropylene glycol 1, 39
    UL-280.07. .
    The ratio of flows A and B (index) is shown in Table 9.
    Gel time at index. 1.03-1.5 s.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing polyurethane urea by reacting the isocyanate component with a polyol, followed by curing the resulting prepolymer with a diamine and a polyol, distinguished by the fact that, in order to increase the gelling time while maintaining the properties of the poly-. urethane ureas, 4,4-methyl en-bis-phenyl isocyanate or the product of its interaction with a mixture of dipropylene glycol and tripropyl glycol, taken at a 1: 1 ratio, and with a polyol selected from the group consisting of polyether mol.m. 1000-6500, polytetramethylene glycol mol.m. 650-2900, polyester mol.m. 500-5600, and the reaction is carried out at a ratio of polyol equivalents to an isocyanate equivalent of 0 „04-0.16, and a 1-methyl-3,5-diztile-2,4-diaminobenzene and 1-metsh1- 3,5Va l-
    1512485JO
    diethyl-2,6-diaminobenzene or 4,4-methylene bis- (2,6-diisopropylaniline) with a ratio of prepolymer to diamine and polyol equal to 0.90-1.17.
    Table 1
    Properties Density, g / cm
    Shore hardness L Modulus of tensile elasticity, kg / cm
    at 100%
    200%
     300%
    Strength at stretching kg / cm Elongation,% Stretching,% Heat leak at, min
    The modulus of elasticity, kg / cm% with
    -29 ° С 24 ° С TO С
    1,02 1,05 1,07 1,08 1,09 1,09 1,10 - .9 52 54 53 53 53 53 53
    126.6 140.6 140.6 140.6 147.7 119.5 112.5 112.5 175.8 196.9 .196.9 203.9 210.9 167.7 154.7 154.7 225 , 0 260.1 260.1 274.2 281.2 - - 246, 1 267.2 281.2 295.3 295.3 203.9 175.8 175.8 350 350 350 300 320 288 280 280
    80 70 70. 70 20
    55
    35 50
    0 0.5 0.3 0.3 0.1 0.1 0.2 0.2
    3660 3460 3760 3850/4240 4020 4860 4560 1168 1287 1443 1240 1532-1460 1228 1137 .719 855 843 778 1327 1138 746 759
    Continuation of table 3
    Table 4
    55
    35 50
    Table3
    17
    Density
    g / cm3 1.10 1.10 1.09 1.12 J, 09 1.12 1.10
    Hardness
    on Shore D 67 68 66 70 -70 71 72
    Elongation,
    % 110 230 110 110 200 150 120
    Break With
    matrices
    % 750 800 820 835 790 775 785
    Table8

    1.08 55 310 660
    0.1
    1.10 55 300 590
    0.0
    Tensile modulus, psi on.
    100% 2200 1950 2100 2200 2200 2400 200% 2950 2600 2800 3000 3050 3250 300% 3900. 3400 3800 - tensile strength,
    pounds / inch 4100 3800 3800 3650 3700 3750 Elongation,% 310 350 300 270 250 240. % 80 83 75 65 70 60
    I
    Table
    1.08 56 310 680
    0.1
    1.07 61 220 680
    1.08 61 200 690
    0.2 0.1 Table9
    nineteen
    1512485
    Editor M.P., Itkina
    Compiled by C, Purina
    Tehred L, Serdyukova Proofreader L. Patay
    Order 5915/59
    Circulation 411
    VNRPSHI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5
    Production and publishing plant Patent, Uzhgorod, st. Gagarin, 101
    20 Continuation of table 9
    Subscription
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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