• 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:
    1390006 Phenoacetals of aromatic 1,2-diketones CIBA-GEIGY AG 27 July 1973 [28 July 1972 28 June 1973] 35844/73 Heading C2C [Also in Division C3] The invention comprises compounds of Formula I wherein R<SP>1</SP> represents C 1 to C 5 alkyl, <SP>C</SP> 2 to C 3 alkenyl, C 7 to C 9 aralkyl, C 8 to C 9 aralkenyl or a group -(CH 2 ) n -X, wherein X represents halogen, OR<SP>3</SP>, -SR<SP>3</SP>, -OAr<SP>3</SP>, -SAr<SP>3</SP>, or n = 1 to 3, R<SP>2</SP> represents a group or -(CH 2 ) 3 -, R<SP>3</SP> represents a C 1 to C 4 alkyl, R<SP>4</SP> represents a C 1 to C 18 alkyl and Ar<SP>1</SP>, Ar<SP>2</SP> and Ar<SP>3</SP> each independently represent a phenyl radical unsubstituted or at most trisubstituted by halogen, alkyl or -O-alkyl having 1 to 4 carbon atoms or by phenyl, or, of Ar<SP>1</SP> or Ar<SP>2</SP> or Ar<SP>1</SP> and Ar<SP>2</SP> represent a phenyl radical substituted as defined, R<SP>1</SP> and R<SP>4</SP> can also represent hydrogen. These compounds of Formula I may be prepared by reacting an aromatic 1,2-diketone either with sulphurous acid ester in the presence of an anhydrous acid and a primary monoalcohol, or with thionyl chloride and a primary monoalcohol.
    公开号:SU751329A3
    申请号:SU742035589
    申请日:1974-06-20
    公开日:1980-07-23
    发明作者:Брюнисхольц Жан；Кирхмайр Рудольф
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the synthesis of polymers by the photopolymerization of unsaturated monomers or polymers. A known method of producing (co) pomers by photopolymerizing non-dried monomers or polymers, or their mixture in the presence of a photosensitizer — about-substituted benzo-alkyl alkyl ester II. The disadvantage of the method is that the polymerization rate is relatively low. The purpose of the invention is the acceleration of the photopolymerization process. To achieve this goal, a method for producing (co) polymers by photopolymerization of unsaturated monomers or polymers, or their mixture in the presence of a photosensitizer, uses a compound of the general formula -CtOCH Tl) where R is hydrogen, C-C5-alkyl, -alkenyl, C-Cd-aralkyl or -CH2X group, in which X is chlorine, bryum or Cf-C-alkoxy, in an amount of 1-20% by weight of unsaturated starting compounds. Photosensitizers are added to photopolymerizable systems, as a rule, by simple intervention, since these systems are in most cases liquid. Almost always occurs the dissolution of photosensitizers in the proposed method, which ensures their uniform distribution and transparency of the polymer. Polymerization of sensitized systems in this way occurs by known methods of photopolymerization by irradiation with light rich in short rays. Suitable light sources for irradiating substrates containing photosensitizers of this formula include medium, high and low pressure emitters, works on mercury, as well as highly emitting fluorescent lamps with a maximum emission in the region of 300-400 mmc. The use of benzyl mono acetals according to the proposed method is described
    further examples, in which all are three by weight.
    Example 1. Photopolymerization of methyl acrylate.
    0.1 g of various known and proposed photosensitizers are dissolved in 10.0 g of freshly distilled acylic acid methyl ester. In a thermostatted water bath (25 ° C), using a high-pressure burner working on vaporous mercury, this solution is illuminated and placed in a quartz glass tube 1.5 cm in diameter. The lamp is located 10 cm from the quartz tube. Nitrogen is passed through the sensitizer solution for 1 min prior to illumination, which continues during illumination. The commencement of polymerization of the monomer during illumination is expressed by an increase in the temperature of the illuminated solution. Lighting time 20 s. Immediately after illumination, cool the illuminated solution to prevent thermal polymerization. The solution of the resulting polymerizate in the monomer is washed off with a small amount of Egl acetate in a round bottom flask, after which the solvent and the part of the monomer that has not entered into the polymerization are distilled off in a rotary evaporator. The polymer residue is dried in a vacuum oven at BO-BO and weighed.
    In tab. 1 lists the amounts of polyacrylic acid methyl ester obtained with various photosensitizers (the amount of photosensitizer in each experiment is 1% by weight). .
    Table 1
    sensitization time
    The number of the formed initiator of the state methyl ester of ether, with polyacrylic acid, wt.%
    Without a photosensitizer, the amount of polymerizate is less than 0.1%.
    Given in Table. 1 data show that compared to known photosensitizers, the proposed photosensitizers cause
    polymerization is faster and gives higher polymer yields.
    EXAMPLE 2: Photopolymerization of methyl acrylate.
    The experiment was carried out analogously to example 1, and the solutions of the known and proposed photosensitizers in acrylic acid methyl ester were illuminated. After various light intervals, a sample of the illuminated solution is evaporated, and the polymer residue is dried and weighed. The results of this experiment are shown in Table. 2. In each experiment, the amount of sensitizer is 1 wt.%.
    Table 2
    The amount of the formed polyacrylic acid methyl ester, weight. %
    6.2
    11.8
    Benzoin
    Benzoinisopropyl ether 4.2 7.7 13.4
    Benzyldimethylacetal 8.0 16.1 26.7
    Given in Table. 2, the data show that, compared with the known photosensitizers, the proposed photosensitizers cause polymerization faster and give higher polymer yields.
    PRI me R 3. Curing of polyester resin.
    0.2 parts of the known and proposed photosensitizers are added to the unsaturated polyester resin in the following quantities: 10 parts of the unsaturated polyester resin (polyester, based on maleinate with a styrene content of 35 wt.%), 0.2 parts of a photosensitizer, 0.1 including 10% paraffin solution in toluene.
    This mixture is stirred until complete dissolution and is then applied with a film former (500 mmk) to glass lamellae. The films are illuminated with a fluorescent lamp with a high proportion of UV radiation, located at a distance of 5 cm. After 20 min of illumination, the hardness of the films is determined using a miniature instrument (a Koenig hardness). The results of the experiments are given in Table. 3
    Table 3 Photosensitizer Solidification of boric acid after 20 substances Benzoin55 Benzoinisopropyl ether. 82 Benzyldimethylacetal 95 Benzyldiethylacetal 93 Benzyldipropylacetal86
    Continued table. 3
    n
    Table Benzyldibutylacetal 90 Benzyldy- / 5-methoxyethyl acetal 83 Example 4. Strength test when stored in a dark place. When a 2% solution of the known and proposed photovibrators in a non-polyethylene polyester resin (malinate-based polyester with a styrene content of 35%) is made, the time it takes for a certain amount of solution to flow through the graduated burette is determined. The solution is stored at room temperature in a dark place and after 2.4 and 8 weeks of storage the flow time through the burette is determined in the same way. For comparison, additive free polyester resin is also tested. The results of the experiments are given in Table. four.
    Polyester resin without additives
    Benzoin
    Benzoinisopropyl
    ether. 272
    Benzyldimethylacetal 265 The same mixtures were stored in the dark for, determined time to gelatinization, which is given in Table 5. Table 5 Photosensitizer Storage time at 60 ° C until gelation, h
    Benzoin 70
    Benzoinisopropyl
    ether190
    Benzyldimethylacetal 230
    Example 5. Curing printing inks.
    275 265 283 278 268 267 284 296
    278 281 283 270 280 280 45 50
    cei The same thing happens if you use the same amount of benzyldimethyl acetal, benzyldibutyl acetal or benzyl di-f5-boroethyl acetal instead of methoxyethyl acetal.
    60 Example 6. Photopolymerization of methyl acrylate.
    Under the conditions described in example 1, methyl acrylate with the addition of 1% of those given in table. 6 photosensitizations 65. Torsors are irradiated for 20 s and a Mixture of 70 parts of trimethyl-propane-trisacrylate, 10 parts of diallyl phthalate prepolymer and 20 parts of benzyl-di- / 3-methoxyethyl acetal serving as a binding agent for inorganic and organic pigments is set and solidifies when irradiated with a high working on mercury for less than 1 hour.
    the amount of polymerizate thus obtained.
    b
    13.5
    17 14.5
    4.5
    Continued table. 7
    I
    Benzyl di- (2-phenoxyethyl) acetal83
    Benzyl di (2-butoxyethyl) acetal90
    Benzyl-di- (2-allyloxyethyl) acetal70
    Benzyldiallyl acetal 74
    Benzyl di- (chloroethyl
    ace.tal81
    Thus, the proposed method produces (co) polymers at a high rate.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing (co) polymers by photopolymerization of non-monomers or polymers or their mixture in the presence of a photosensitizer, characterized in that, in order to accelerate the photopolymerization process, a compound of the general formula is used as a photosensitizer
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    同族专利:
    公开号 | 公开日
    NL7310297A|1974-01-30|
    DK152726B|1988-05-02|
    DE2337813A1|1974-02-07|
    DK152726C|1988-10-24|
    DE2365852B2|1981-02-19|
    FR2194698B1|1976-09-17|
    FR2194698A1|1974-03-01|
    ES417307A1|1976-06-01|
    GB1390006A|1975-04-09|
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    DE2365852C3|1981-10-15|
    DE2365497A1|1975-04-24|
    FI60194C|1981-12-10|
    SE417426B|1981-03-16|
    JPS4955646A|1974-05-30|
    DE2337813C3|1981-11-19|
    FI60194B|1981-08-31|
    AU5830773A|1975-01-23|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH1129572A|CH575965A5|1972-07-28|1972-07-28|Aromatic 1,2-diketone monoacetals - useful as photoinitiators and cross-linking agents|
    CH941773A|CH587867A5|1973-06-28|1973-06-28|Aromatic 1,2-diketone monoacetals - useful as photoinitiators and cross-linking agents|
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