• 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:
    Novel allyl-acrylic monomers of the formula: <IMAGE> wherein R is a C1-4 alkylene group and R1 is hydrogen or methyl, are described. The preferred monomer is that in which R is ethylene and R1 is methyl. When subjected to conventional free radical polymerization, in one stage or two stages, these monomers give transparent polymers having good mechanical properties, particularly hardness.
    公开号:SU878193A3
    申请号:SU772518000
    申请日:1977-09-07
    公开日:1981-10-30
    发明作者:Сене Жан-Пьер；Ле Руа Патрис
    申请人:Сосьете Насьональ Де Пудр Э Эксплозиф (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING ACRYLIC OR METHACRYLIC ACID ESTERS The invention relates to a process for the preparation of new chemical compounds, specifically to a process for the preparation of acrylic or methacrylic acid esters of the general formula-, CTj :: CH-CH2 CNa r-2.2 2 600 where R - an alkyl group containing from 1 to 4 carbon atoms; R is hydrogen or methyl, which can be used as monomers for the preparation of transparent polymers. These polymers are used to produce such transparent products as panels, pane glass, windshield, structural elements, etc. The most well-known representative of monomers of this type is allyl carbonate ethylene glycol methacrylate {1 of the formula Sig CH-CH20CO (CHg) 20 C-C GH2 oo Car Another known monomer for the production of transparent polymers is the allimer C.P. 149 (the trade mark of the form Petsburt Plast Glass and To ) Formulas CI2 CH-CIl20CJNll (CH2) 20CO {CH2) NHCOCai20 O-GH-CH2 Based on this monomer, organic glasses are obtained that have good hardness, bending strength and high abrasion resistance. 2. The purpose of the invention is to develop a process for the preparation of new acrylic esters oretakrilovoy acid of formula (I) with improved mechanical properties. The proposed method is based on the known reaction of reacting organochlorine compounds with alcohols to form an ether linkage 3 and consists in the fact that the chloroformate derivative of the formula, CH2 C3t-CB2-OCNH-B-OCCl. SchO O is condensed with a compound of the formula CHg-C-C 0 - () 20D () Bj O where R and K are as defined above, in the presence of a mixture of pyridine and dichloromethane. The chloroformate derivative of the formula III is obtained by the interaction of allyl chloroformate with the corresponding hydroxy alkylamine, and then the resulting compound. Formulas СН2 СН - СНг-ОС -TOCHON (j О is treated with phosgene. The most preferred monomer of formula I is the compound with R - (СН2) 2 - and R СН. Example 1. Preparation of the monomer of formula 1cK - ( CH2) 2, - and R. CH3 a} Condensation of allyl chloroformate with monoethanolamine 73.2 g of C 2 mol of monoethanolamine and 200 ml of anhydrous diethyl ether are introduced into a reactor equipped with a stirrer, a thermometer, a suction tube and a dropping funnel. Cooling give the content to about C and then slowly pour 60.25 g (0.5 mol) of allyl chloroformate with stirring. The temperature of the reaction mixture n must exceed (the duration of pouring of the allyl chloroformate is 2 hours). Stirring is carried out for 1 hour and then the contents are treated with a stream of anhydrous hydrochloric acid until absorption is stopped. The monoethanolamine hydrochloride obtained is isolated by filtration, the solvent is removed by evaporation under reduced pressure. 53 g (yield 73% relative to allyl chloroformate) of a yellow oil (compound Y) are obtained. B) Phosgenization of compound Y, 50 g of liquid phosgene are introduced into the reactor, equipped with a condenser (down to -40 ° C), a stirrer, a tube for pouring and thermometer. Then, while stirring, 43.5 (OJ3 mol) of the compound obtained previously is slowly poured. The temperature of the reaction medium is maintained at values from -15 to -10 during the entire casting period. Chloroformate is purified from excess phosgene and dissolved hydrochloric acid by sparging. nitrogen with stirring. Obtain 52 g (yield 84%) of a slightly yellow oil (compound GP). The infrared spectrum is in accordance with the assumed assumed structure of the compound. The measured chlorine content is 16.7% (theoretical 17.1%). c) Condensation of chloroformate (III) with 2-hydroxyethyl methacrylate. 26 g (0.2 mol) of 2-hydroxyethyl methacrylate stabilized with 100 h / min of hydroquinone, 18.9 g (0.24 mol) of pyridine and 60 ml of anhydrous dichloromethane are introduced into a reactor equipped as described above. The contents are cooled to and poured with stirring for about 2 hours to 41.5 g (0.2 mol) of compound III, while maintaining the temperature from +5 to. Stirring is continued for 1 hour at + 5 ° C, then 100 ml of distilled water is added. The organic phase is defended, washed in 100 ml of 2N. solution of hydrochloric acid, and then in final water to obtain wash water with a neutral reaction. After drying on anhydrous sodium sulfite and evaporation of the solvent under reduced pressure (temperature not higher than 30 ° C), 55 g of anhydrous oil, i.e. the yield is 91%, which is the desired product. EXAMPLE 2. Preparation of a monomer of formula 1c R - (CH2) z and R CH3. In a reactor equipped with a stirrer, a thermometer, a dip tube and a dropping funnel, 11.6 g (0.1 mol) of 2-hydroxy are introduced. -ethyl acrylate, stabilized 100 parts per million of hydroquinone, 10 g (0.126 mol) of anhydrous pyridine, 60 cm of dry dichloromethane. The mixture was maintained at 0 ° C, 21 g (0.1 mol) of the compound of formula III was added with stirring for 1 hour and dissolved in 40 cm of dichloromethane. After 1 hour of stirring at room temperature, 80 cm of distilled water are added. The organic phase is decanted, washed with acidified water, then with pure water, dried and evaporated at 25 s. 25 g of a colorless oil are obtained in this way, the yield is 87%. Froze The preparation of a monomer of formula I with R - (CH2) 4 R t HdOperates as in example 1, but comes from the corresponding chloroformate derivative of the formula III and 2-hydroxyethyl methacrylate. The structure of the final and intermediate HEJX products was confirmed by the data of IR and NMR spectroscopy. New monomers in the polymerization process result in transparent polymers with high mechanical properties and hardness. Below are examples of the implementation of polymerization using monomers of the formula I, in which the characteristics of polymers are given. PRI me R 4. 1st stage. 135 g of monomer according to Example 1 is mixed with 765 g of chloroform. The mixture was kept at 50 ° C, and then 0.1844 g of benzoyl peroxide was dissolved in the mixture. The polymerization is carried out in a reactor under a stream of nitrogen, maintaining constant mixing of the mixture. After 10 hours, the polymer is precipitated in ethanol, then filtered off and dried. The degree of monomer conversion to polymer is 30%. The characteristics of the polymer obtained are as follows: Molecular weight 150000 Polydispersity 3 Glass transition temperature, C23 Forming conditions: temperature 180 ° C; pressure 100 bar, time 5 m transparency is good. . Stage 2 2% 1, 3-bis- (tert, butylperoxyisopropyl) -benzene is added to the polymer obtained in Step 1. The product is then molded under pressure at 170 ° C for 5 minutes and then calcined for 2 hours at. The plate thus obtained is transparent, the hardness is 44 Barcol points, the density is 1.354. PRI me R 5. 1st stage. 150 g of monomer are mixed with 750 g of chloroform; the mixture is kept at 50 ° C and then 0.1844 g of besoyl benzoyl peroxide is dissolved in it. After 24 hours polymerization, 75 grams of polymer is re-precipitated in ethanol (i.e. a conversion rate of 50%. The molecular weight of the obtained polymer is very high (500,000), glass transition temperature. 2nd step, after adding 2% 1, 3-bis- (tert.butylperoxyisopropyl) -benzene, the product is molded at 180 s for 5 minutes, calcined for 2 hours at 110 ° C, the polymerization is completed and a transparent and solid product is obtained (45 Barkol points), density is 1,350 5 g of cyclohexyl percarbonate is dissolved in 100 g of monomer. This solution is then poured into a mold formed Glass plates separated by a plastic partition with a thickness of J mm. The mold is then placed in a water bath and subjected to the following thermal effect: 48 hours at 40 ° C, 1 hour at 1 hour at 1 hour 30 minutes at 80s, 2 hours at 3 The resulting material, taken out of the mold, has the following characteristics: Transparency Good Hardness of the Barcol point 44 Density 1,354 Strength in tension, g bar 3.30 Young modulus gbar 121 Example7. 1 g of cyclohexyl percarbonate is mixed with 100 g of monomer. This solution is then poured into a mold formed by two glass plates separated by a 3 mm thick plastic partition. The form is placed in a water bath and subjected to the following thermocondition: 15 hours at 1 hour at 50 ° C, 1 hour at 1 hour 30 minutes at 8 (f C, 2 hours at 3. hours at 115 ° C. Obtained and extracted the material has the following properties from the form: transparency is good; hardness is 54 Barkol points; density is 1.351. From the description of the above examples, it is clear that transparent polymers can be obtained from onomers with interesting mechanical properties and hardness. , inexx refraction and resistance to the gap / polyme as described in Prieuré allimera form (II). The table shows that the density of the index of refraction for the two sravni1y olimerov, however, polymers prepared on the basis of new monomers have Warmer soprotivenie strength and tear than known.
    Density
    Strength, units Barkol
    Refraction index at
    Tear resistance, kg / cm
    1,351
    1,332 54 48
    1.512
    权利要求:
    Claims (1)
    [1]
    1.512 550 327 787819 Claim 1 Invention of the preparation of esters of acrylic or methacrylic acid of the formula BI CH4 "CB-CHeOCra-II OC-p (t)., 5 in -LV. where R is an alkyl group containing from 1 to 4 carbon atoms and R is hydrogen or methyl, tO characterized in that the chloroformate derivative of the formula iCM9 -CII-CHo-OCNH-Ri- "OCCl. 15 IIN 11 and 38 where R has the above values is condensed with a compound of the formula - (cp1 OH I II 2 i 1 has the above value i Q in the presence of a mixture of pyridine and dichloromethane. Sources of information taken into account in the examination 1. US patent No. 2384115, 260-77.5, published 1946. U.S. Patent No. 2,339,631, class 260-77.5, published 1946. HDCOH d. Organic syntheses. Part 1, M., Mir, 1973, ChbSKI iTUTCiOLT U1M Mtlgch 1 s 343.
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    同族专利:
    公开号 | 公开日
    DE2740271C2|1982-05-27|
    NL7709579A|1978-03-09|
    IT1090853B|1985-06-26|
    SU826960A3|1981-04-30|
    FR2363546A1|1978-03-31|
    IE45370L|1978-03-07|
    CA1088092A|1980-10-21|
    US4241202A|1980-12-23|
    DE2740271A1|1978-03-16|
    JPS5654311B2|1981-12-24|
    JPS5915327B2|1984-04-09|
    JPS5359624A|1978-05-29|
    DK394977A|1978-03-08|
    LU78078A1|1978-01-18|
    US4199526A|1980-04-22|
    NL172444C|1983-09-01|
    IE45370B1|1982-08-11|
    NL172444B|1983-04-05|
    FR2363546B1|1979-01-12|
    GB1542553A|1979-03-21|
    BE858481A|1978-03-07|
    JPS5695911A|1981-08-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2397631A|1944-02-07|1946-04-02|Pittsburgh Plate Glass Co|Unsaturated carbamate|
    US2441298A|1944-03-29|1948-05-11|Pittsburgh Plate Glass Co|Unsaturated esters|
    US2568608A|1947-03-19|1951-09-18|Goodrich Co B F|Polyunsaturated nitrogen-containing compounds and polymers thereof|
    US2579426A|1947-07-26|1951-12-18|Wingfoot Corp|Allyl amine carbonates, polymers, and copolymers|
    US2579427A|1947-09-09|1951-12-18|Wingfoot Corp|Allyl carbonates, polymers, and copolymers|
    DE1251956B|1964-12-30|1967-10-12|Farbenfabriken Bayer Aktienge Seilschaft, Leverkusen|Process for the production of homo- or copolymers|
    SU445316A1|1972-02-21|1976-07-05|Ордена Ленина Институт Химической Физики Ан Ссср|The method of obtaining compounds with urethane groups|
    DE2365631A1|1973-02-12|1975-10-30|I Khim Fiz Akademii Nauk Ssr|Urethane-acrylate oligomers - prepd. from chloroformates of acrylates and amines|
    DE2336264A1|1973-07-17|1975-02-20|Kansai Paint Co Ltd|Photopolymerisable divinyl-urethane monomers - from xylylene diisocyanate, for tough, abrasion-resistant printing plates, giving rapid hardening and easy development|
    DE2422170C2|1974-05-08|1982-09-23|Bayer Ag, 5090 Leverkusen|Polymerizable N, N-disubstituted carbamoyloxyalkylcarboxylic acid esters, process for their preparation and their use|
    US3953544A|1974-05-10|1976-04-27|Trw Inc.|Low temperature curing adhesives|
    JPS5311314B2|1974-09-25|1978-04-20|US4360653A|1981-10-23|1982-11-23|Ppg Industries, Inc.|Polymerizate ofand aliphatic polyurethane having acrylic unsaturation|
    IT1151544B|1982-04-15|1986-12-24|Anic Spa|COMPOSITION BASED ON ALIPHATIC POLYCARBONATES CONTAINING URETHANE GROUPS AND ACRYLIC OR METHACRYLIC TERMINATIONS CROSS-LINKED IN THE PRESENCE OF ROOTIC INITIATORS|
    JPS59112017U|1982-06-02|1984-07-28|
    JPH0316497Y2|1984-06-09|1991-04-09|
    US5144056A|1985-12-03|1992-09-01|Atochem|Fluorinated acrylic monomers as hydrophobic and oleophobic agents|
    FR2590895B1|1985-12-03|1988-01-15|Atochem|FLUORINATED ACRYLIC MONOMERS, DERIVATIVE POLYMERS AND THEIR APPLICATION AS HYDROPHOBIC AND OLEOPHOBIC AGENTS|
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    JPH033207Y2|1987-04-17|1991-01-28|
    JPH0199236U|1987-12-24|1989-07-03|
    BR9000916A|1989-03-01|1991-02-13|Mitsui Toatsu Chemicals|PROCESS FOR THE PREPARATION OF A TRANSPARENT RESIN OF HIGH HARDNESS, PROCESS FOR THE PREPARATION OF A POLYMERIZABLE MONOMER, VITREO MATERIAL, PROTECTIVE COVER FOR DISPLAY DEVICES, OPTICAL LENS, HARD COVER MATERIAL AND A HARDWARE PROCESSING MATERIAL|
    US5260439A|1989-03-01|1993-11-09|Mitsui Toatsu Chemicals, Incorporated|Polymerizable monomer having at least one isopropenyl phenyl group and being capable of forming a high surface hardness transparent resin|
    GB9001405D0|1990-01-22|1990-03-21|Leo Pharm Prod Ltd|New intermediates,their production and use|
    US5159098A|1990-09-10|1992-10-27|Isp Investments Inc.|Alk-1-enyloxy carbamates|
    IL124933D0|1997-07-23|1999-01-26|Premark Rwp Holdings Inc|Thermoplastic acrylic sheet compositions and their use as substitutes for high pressure laminate|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7626913A|FR2363546B1|1976-09-07|1976-09-07|
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