CN1073580C - Rigidity plastics based on isocyanate and preparing method thereof - Google Patents
Rigidity plastics based on isocyanate and preparing method thereof Download PDFInfo
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- CN1073580C CN1073580C CN97106367A CN97106367A CN1073580C CN 1073580 C CN1073580 C CN 1073580C CN 97106367 A CN97106367 A CN 97106367A CN 97106367 A CN97106367 A CN 97106367A CN 1073580 C CN1073580 C CN 1073580C
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 27
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229920003023 plastic Polymers 0.000 title claims abstract description 17
- 239000004033 plastic Substances 0.000 title claims abstract description 17
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- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
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- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical group OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 2
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- JEQBFCJBVVFPGT-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C=CC=C2)C2=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C=CC=C2)C2=C1 JEQBFCJBVVFPGT-UHFFFAOYSA-N 0.000 claims 1
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- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
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- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
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- 238000006297 dehydration reaction Methods 0.000 description 2
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- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明公开了一种以异氰酸酯为基的刚性塑料，其特征为：由二元醇R1和二元酸以1.5/1-2.0/1的醇酸摩尔比进行反应得到羟基封端的不饱和聚酯树脂，再用占该聚酯重量百分比20-50%的交联剂R4与不饱和聚酯树脂的加聚反应及不饱和聚酯树脂上的羟基与指数为90-120的异氰酸酯R2间的缩聚反应生成一个体型网络结构，本发明工艺简单，固化时间短，并具有优异的力学性能、热性能和电性能，开拓了聚氨酯材料作为灌封绝缘材料的应用领域。The invention discloses a rigid plastic based on isocyanate, which is characterized in that a hydroxyl-terminated unsaturated polymer is obtained by reacting dibasic alcohol R1 and dibasic acid at an alkyd molar ratio of 1.5/1-2.0/1. ester resin, and then use the polyaddition reaction of crosslinking agent R 4 and unsaturated polyester resin accounting for 20-50% by weight of the polyester and the hydroxyl group on the unsaturated polyester resin and the isocyanate R 2 whose index is 90-120 The polycondensation reaction among them generates a body-shaped network structure. The invention has simple process, short curing time, excellent mechanical properties, thermal properties and electrical properties, and opens up the application field of polyurethane materials as potting insulation materials.
Description
本发明涉及化工方面的高分子的合成技术，具体地说是一种以异氰酸酯为基的刚性塑料及其制备方法。The present invention relates to the synthesizing technology of macromolecule in chemical industry, specifically a kind of isocyanate-based rigid plastic and its preparation method.
传统的电器灌封绝缘材料是环氧树脂，这种材料以其优异的热性能和电性能在电器灌封绝缘材料领域独领风骚，但环氧树脂生产周期长，材料韧性差也一直是生产行业需亟待解决的问题，聚氨酯自从被开发利用以来，由于其生产周期短和特殊的物化性能，在人们生活中占据了重要的位置，但其耐电、耐热性能达不到电器灌封材料的要求。许多年来，人们利用各种手段在环氧树脂和聚氨酯的改性方面做了大量的工作，例如利用聚氨酯的韧性结构使它分别与不饱和聚酯、乙烯基酯树脂作成互穿网络，还有人利用异氰酸酯与环氧树脂反应制得高耐热的噁唑烷酮，都使聚氨酯材料的性能有了大幅度的提高，但这些方法工艺复杂，价格昂贵，难以实现工业化，不利于广泛应用。The traditional electrical potting insulation material is epoxy resin. This material is unique in the field of electrical potting insulation materials due to its excellent thermal and electrical properties. However, the production cycle of epoxy resin is long and the toughness of the material is poor. The industry needs to solve the problem urgently. Since polyurethane was developed and utilized, due to its short production cycle and special physical and chemical properties, it occupies an important position in people's life, but its resistance to electricity and heat is not as good as that of electrical potting materials. requirements. For many years, people have done a lot of work on the modification of epoxy resin and polyurethane by using various means, such as making use of the tough structure of polyurethane to make it interpenetrate with unsaturated polyester and vinyl ester resin respectively. The high heat-resistant oxazolidinone prepared by the reaction of isocyanate and epoxy resin has greatly improved the performance of polyurethane materials, but these methods are complicated in process, expensive, difficult to realize industrialization, and unfavorable for wide application.
本发明的目的在于提供一种以异氰酸酯为基的刚性塑料，它能克服现有技术中的不足。The object of the present invention is to provide a rigid plastic based on isocyanate, which can overcome the deficiencies in the prior art.
本发明的技术方案是这样实现的：以异氰酸酯为基的刚性塑料其特征在于：由二元醇R1与由不饱和二元酸(或酸酐)和饱和二元酸(或酸酐)以1∶1摩尔比组成的混合物以1.5/1～2.0/1的醇酸摩尔比进行反应得到羟基封端的不饱和聚酯树脂，再用占该聚酯重量百分比20～50％的交联剂R4与不饱和聚酯树脂的加聚反应及不饱和聚酯树脂上的羟基与指数为90～120的异氰酸酯R2间的缩聚反应生成一个体型网络结构，其化学结构为：
以异氰酸酯为基的刚性塑料的制备方法，其特征在于：a．酯化反应合成端羟基不饱和聚酯树脂，方法如下：先将系统用干燥氮气清洗，再根据设计的不饱和聚酯树脂的分子量的大小加入1.5/1～2.0/1的醇酸摩尔比的二元醇R1及由不饱和二元酸(或酸酐)和饱和二元酸(或酸酐)以1/1摩尔比组成的混合物，在180～220℃下进行酯化反应，当反应混合物的酸值降至5mgKOH/g时，将系统抽真空至0～2mmHg，使酯化反应继续进行并抽出小分子的水和未反应的小分子醇，当酸值降至低于0.5mgKOH/g时，视为反应结束。测量不饱和聚酯树脂的羟值并计算出分子量；b．复合反应生成单网络，其工艺条件如下：将不饱和聚酯树脂进行脱水，工艺条件为：温度80～95℃、压力0～2mmHg、时间2～4小时；再加入交联剂R4稀释，降低物料温度，交联剂按不饱和聚酯树脂重量百分比的20～50％加入并搅拌混匀；物料温度冷却至20℃下，加入不饱和聚酯和交联剂总量的0.5～2％重量百分比的引发剂及指数为90～120的异氰酸酯R2，抽真空至0～2mmHg并快速搅拌1分钟左右，停止搅拌并继续抽真空至物料中无气泡出现后停止抽真空，将物料浇铸到预热至80～90℃的模具中；进行固化及后熟化工艺如下：在80～90℃的烘箱中固化6～10分钟后启模，再送入100℃的烘箱中，后熟化1～2小时。A method for preparing a rigid plastic based on isocyanate, characterized in that: a. Synthesis of hydroxyl-terminated unsaturated polyester resin by esterification, the method is as follows: first clean the system with dry nitrogen, and then add alkyd molar ratio of 1.5/1 to 2.0/1 according to the molecular weight of the designed unsaturated polyester resin Dibasic alcohol R 1 and a mixture composed of unsaturated dibasic acid (or acid anhydride) and saturated dibasic acid (or acid anhydride) in a molar ratio of 1/1, undergo esterification reaction at 180-220°C, when the reaction mixture When the acid value drops to 5mgKOH/g, vacuum the system to 0-2mmHg to continue the esterification reaction and extract small molecules of water and unreacted small molecules of alcohol. When the acid value drops below 0.5mgKOH/g , which is considered as the end of the reaction. Measure the hydroxyl value of unsaturated polyester resin and calculate the molecular weight; b. Composite reaction to form a single network, the process conditions are as follows: dehydrate the unsaturated polyester resin, the process conditions are: temperature 80 ~ 95 ℃, pressure 0 ~ 2mmHg, time 2 ~ 4 hours; then add crosslinking agent R 4 to dilute, Lower the temperature of the material, add the cross-linking agent according to the weight percentage of 20-50% of the unsaturated polyester resin and stir and mix; cool the material temperature to 20°C, add 0.5-2% of the total amount of the unsaturated polyester and cross-linking agent Initiator by weight percentage and isocyanate R 2 with an index of 90-120, vacuumize to 0-2mmHg and stir rapidly for about 1 minute, stop stirring and continue vacuuming until no bubbles appear in the material, then stop vacuuming, and cast the material into Preheat to a mold at 80-90°C; carry out curing and post-curing process as follows: open the mold after curing in an oven at 80-90°C for 6-10 minutes, then put it into an oven at 100°C, and post-cure for 1-2 hours .
本发明先合成分子量为100～2000的羟基封端不饱和聚酯树脂HUPR，经交联剂稀释，与异氰酸酯反应，在同一反应体系中同时利用形成氨基甲酸酯的缩聚反应和形成不饱和聚酯网络的加聚反应，一步法合成出具有单网络结构的刚性塑料，这种独特的化学结构赋予该新材料优异的力学性能、热性能和电性能。本发明工艺简单，固化时间短，且由于混合物料的粘度低，需要时可以填充石英粉等无机填料以降低成本，开拓了聚氨酯作为灌封绝缘材料的应用领域，加速灌封绝缘材料技术的发展。In the present invention, the hydroxyl-terminated unsaturated polyester resin HUPR with a molecular weight of 100-2000 is firstly synthesized, diluted with a cross-linking agent, reacted with isocyanate, and utilizes the polycondensation reaction of forming carbamate and the formation of unsaturated polymer in the same reaction system at the same time. The polyaddition reaction of the ester network can synthesize a rigid plastic with a single network structure in one step. This unique chemical structure endows the new material with excellent mechanical properties, thermal properties and electrical properties. The invention has simple process, short curing time, and due to the low viscosity of the mixed material, if necessary, it can be filled with inorganic fillers such as quartz powder to reduce the cost, opens up the application field of polyurethane as potting insulating material, and accelerates the development of potting insulating material technology .
下面对本发明做进一步的描述并给出实施例。The present invention is further described and examples are given below.
本发明是一种以异氰酸酯为基的刚性塑料，其特征在于：由二元酸R1与由不饱和二元酸(或酸酐)和饱和二元酸(或酸酐)以1∶1摩尔比组成的混合物以1.5/1～2.0/1的醇酸摩尔比进行反应得到羟基封端的不饱和聚酯树脂，再用占该聚酯重量百分比20～50％的交联剂R4与不饱和聚酯树脂的加聚反应及不饱和聚酯树脂上的羟基与指数为90～120的异氰酸酯R2间的缩聚反应生成一个体型网络结构，其化学结构为：
其中：R1为二甘醇、2-甲基-1,3-丙二醇、1,4-丁二醇、乙二醇、1,2-丙二醇，或者上述二元醇的混合物；异氰酸酯R2为甲苯二异氰酸酯TDI、二苯基亚甲基二异氰酸酯MDI、多苯基多亚甲基多异氰酸酯PAPI、萘二异氰酸酯NDI、六亚甲基二异氰酸酯HDI或改性MDI；饱和二元酸R3为邻苯二甲酸、对苯二甲酸、邻苯二甲酸酐、己二酸；交联剂R4为苯乙烯、其他苯的乙烯基衍生物、邻苯二甲酸二烯丙酯DAP。Wherein: R 1 is diethylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, ethylene glycol, 1,2-propanediol, or a mixture of the above diols; isocyanate R 2 is Toluene diisocyanate TDI, diphenylmethylene diisocyanate MDI, polyphenyl polymethylene polyisocyanate PAPI, naphthalene diisocyanate NDI, hexamethylene diisocyanate HDI or modified MDI; saturated dibasic acid R 3 is Phthalic acid, terephthalic acid, phthalic anhydride, adipic acid; crosslinker R4 is styrene, other vinyl derivatives of benzene, diallyl phthalate DAP.
以异氰酸酯为基的刚性塑料的制备方法是，先利用酯化反应合成羟基封端的不饱和聚酯，它的化学反应简式：
其中R1为二元醇，R3为饱和二元酸。二元醇与二元酸的投料比根据设计的不饱和聚酯树脂的分子量确定，不饱和聚酯树脂的分子量一般为100～2000。先将系统用干燥氮气清洗，再根据设计的不饱和聚酯树脂的分子量的大小加入1.5/1～2.0/1的醇酸摩尔比的二元醇R1及由不饱和二元酸(或酸酐)和饱和二元酸(或酸酐)以1/1摩尔比组成的混合物，在180～220℃下进行酯化反应，当反应混合物的酸值降至5mgKOH/g时，将系统抽真空至0～2mmHg，使酯化反应继续进行并抽出小分子的水和未反应的小分子醇，当酸值降至低于0.5mgKOH/g时，即反应程度至99.8％以上时视为反应结束。测量不饱和聚酯树脂的羟值并计算出分子量；再复合反应生成单网络，反应简式如下：Wherein R1 is dibasic alcohol, R3 is saturated dibasic acid. The feeding ratio of dihydric alcohol and dibasic acid is determined according to the molecular weight of the designed unsaturated polyester resin, and the molecular weight of the unsaturated polyester resin is generally 100-2000. First clean the system with dry nitrogen, and then add diol R1 with an alkyd molar ratio of 1.5/1 to 2.0/1 and unsaturated dibasic acid (or anhydride) according to the molecular weight of the unsaturated polyester resin designed. ) and saturated dibasic acid (or acid anhydride) in a 1/1 molar ratio, carry out esterification reaction at 180-220°C, when the acid value of the reaction mixture drops to 5mgKOH/g, vacuum the system to 0 ~2mmHg, to continue the esterification reaction and extract small molecules of water and unreacted small molecules of alcohol. When the acid value drops below 0.5mgKOH/g, that is, when the reaction degree reaches above 99.8%, the reaction is considered to be over. Measure the hydroxyl value of the unsaturated polyester resin and calculate the molecular weight; recombination reaction to form a single network, the reaction is as follows:
(1)氨酯化反应生成聚氨酯长链：
具体操作步骤如下：The specific operation steps are as follows:
(1)不饱和聚酯树脂的脱水。工艺条件如下：(1) Dehydration of unsaturated polyester resin. The process conditions are as follows:
温度80～95℃、压力0～2mmHg、时间2～4小时。The temperature is 80-95°C, the pressure is 0-2mmHg, and the time is 2-4 hours.
(2)加入交联剂稀释，降低物料温度，交联剂按不饱和聚酯树脂重量百分比的20～50％加入并搅拌15～20分钟混匀。(2) adding a cross-linking agent for dilution, lowering the temperature of the material, adding the cross-linking agent according to 20-50% by weight of the unsaturated polyester resin and stirring for 15-20 minutes to mix.
(3)物料温度冷却至20℃以下，加入不饱和聚酯和交联剂总重量的0.5～2％的引发剂及指数为90～120的异氰酸酯，抽真空至0～2mmHg并快速搅拌1分钟，停止搅拌并继续抽真空2～3分钟至物料中无气泡出现后停止抽真空，并将物料浇铸到预热至80～90℃的模具中。(3) Cool the temperature of the material to below 20°C, add 0.5-2% of the total weight of the unsaturated polyester and crosslinking agent as an initiator and an isocyanate with an index of 90-120, vacuumize to 0-2mmHg and stir rapidly for 1 minute , stop stirring and continue vacuuming for 2-3 minutes until no air bubbles appear in the material, then stop vacuuming, and cast the material into a mold preheated to 80-90°C.
(4)固化条件及后熟化工艺。(4) Curing conditions and post-curing process.
固化条件：80～90℃的烘箱中固化6～10分钟后启模。Curing conditions: Curing in an oven at 80-90°C for 6-10 minutes before opening the mold.
后熟化工艺：将样品送入100℃的烘箱中，后熟化1～2小时。Post-curing process: put the sample into an oven at 100°C, and post-cure for 1 to 2 hours.
为了进一步证明本发明的工艺过程，例举如下实施例及产品的性能。In order to further prove the technical process of the present invention, the performance of the following examples and products is given for example.
实施例1，以一缩二乙二醇为二元醇的不饱和聚酯及其刚性塑料的制备。Embodiment 1, the preparation of unsaturated polyester and its rigid plastic with diethylene glycol as glycol.
步骤1，进行酯化反应合成不饱和聚酯树脂(HUPR1)，Step 1, carry out esterification reaction synthetic unsaturated polyester resin (HUPR1),
(1)所用的二元酸(酐)是由邻苯二甲酸酐和顺丁烯二酸酐以1/1的摩尔比组成；(1) The dibasic acid (anhydride) used is composed of phthalic anhydride and maleic anhydride in a molar ratio of 1/1;
(2)二甘醇与酸酐以1.5/1的摩尔比投料；物料配比：一缩二乙二醇4.26摩尔(452.13g)邻苯二甲酸酐1.42摩尔(210.16g)顺丁烯二酸酐1.42摩尔(139.16g)(2) Diethylene glycol and acid anhydride are fed at a molar ratio of 1.5/1; material ratio: 4.26 moles of diethylene glycol (452.13g) 1.42 moles of phthalic anhydride (210.16g) 1.42 moles of maleic anhydride Mole (139.16g)
首先将系统用干燥氮气清洗，再加入二甘醇和苯酐，在180℃下反应，通过测定反应生成物的酸值，当反应程度至60％时，降低体系的温度至100℃，加入顺酐，180℃下反应1.5小时，200℃下反应2小时，210℃下反应2小时，220℃下反应1小时，至酸值降至5mgKOH/g时停止加热；First, clean the system with dry nitrogen, then add diethylene glycol and phthalic anhydride, and react at 180°C. By measuring the acid value of the reaction product, when the reaction degree reaches 60%, reduce the temperature of the system to 100°C, and add maleic anhydride. React at 180°C for 1.5 hours, at 200°C for 2 hours, at 210°C for 2 hours, at 220°C for 1 hour, stop heating when the acid value drops to 5 mgKOH/g;
(3)抽真空进一步降低酸值，抽真空至0～2mmHg，逐步升温至200℃，反应3小时并抽出小分子的水和未反应的小分子醇，当酸值降至低于0.5mgKOH/g时视为反应结束；(3) Vacuumize to further reduce the acid value, vacuumize to 0-2mmHg, gradually raise the temperature to 200°C, react for 3 hours and extract small molecule water and unreacted small molecule alcohol, when the acid value drops below 0.5mgKOH/ g is considered as the end of the reaction;
(4)测量不饱和聚酯树脂的羟值并计算出分子量。(4) Measure the hydroxyl value of the unsaturated polyester resin and calculate the molecular weight.
步骤2，以多苯基多亚甲基多异氰酸酯(PAPI)和HUPR1通过复合反应生成单网络，Step 2, using polyphenyl polymethylene polyisocyanate (PAPI) and HUPR1 to generate a single network through a composite reaction,
反应简式如下：The reaction formula is as follows:
(1)氨酯化反应生成聚氨酯长链：
其工艺条件如下：Its technological conditions are as follows:
(1)不饱和聚酯树脂的脱水：(1) Dehydration of unsaturated polyester resin:
温度80～90℃、压力0～2mmHg、时间2～4小时； Temperature 80～90℃, pressure 0～2mmHg, time 2～4 hours;
(2)加入苯乙烯稀释，物料温度控制在80℃，将苯乙烯按一定比例加到不饱和聚酯树脂中，搅拌20分钟混匀；(2) Add styrene for dilution, control the material temperature at 80°C, add styrene in a certain proportion to the unsaturated polyester resin, stir for 20 minutes and mix well;
(3)加入引发剂及异氰酸酯，物料温度冷却至20℃以下，加入不饱和聚酯和苯乙烯总重量的1％的引发剂及指数为105的异氰酸酯PAPI，抽真空至2mmHg并快速搅拌1分钟，停止搅拌并继续抽真空2～3分钟，至物料中无气泡出现后停止抽真空，将物料浇铸到预热至80℃的模具中；(3) Add initiator and isocyanate, cool the material temperature to below 20°C, add 1% initiator of the total weight of unsaturated polyester and styrene and isocyanate PAPI with an index of 105, vacuumize to 2mmHg and stir rapidly for 1 minute , stop stirring and continue vacuuming for 2 to 3 minutes, stop vacuuming until no air bubbles appear in the material, and cast the material into a mold preheated to 80°C;
(4)固化条件及后熟化工艺：(4) Curing conditions and post-curing process:
固化条件：80℃的烘箱中固化10分钟后启模。Curing conditions: Curing in an oven at 80°C for 10 minutes before opening the mold.
后熟化工艺：将样品送入100℃的烘箱中，后熟化2小时。Post-curing process: put the sample into an oven at 100°C for post-curing for 2 hours.
实施例2，以2-甲基-1,3丙二醇为二元醇的不饱和聚酯及其刚性塑料的制备。Example 2, preparation of unsaturated polyester with 2-methyl-1,3 propanediol as diol and its rigid plastic.
合成羟基封端不饱和聚酯树脂(HUPR2)的配方及工艺：The formula and process of synthesizing hydroxyl-terminated unsaturated polyester resin (HUPR2):
2-甲基-1,3-丙二醇3摩尔(270g)3 moles of 2-methyl-1,3-propanediol (270g)
邻苯二甲酸酐1摩尔(148g)1 mole of phthalic anhydride (148g)
顺丁烯二酸酐1摩尔(98g)不饱和聚酯合成工艺及复合反应合成刚性塑料单网络的工艺与实施例1相同。Maleic anhydride 1 mole (98g) unsaturated polyester synthesis process and composite reaction synthesis rigid plastic single network process is the same as in Example 1.
实施例1、2的配方及性能见下表所示。The formula and performance of embodiment 1,2 are shown in the table below.
实施例1、2的配方、性能一览表
b)HUPR1指以一缩二乙二醇为二元醇合成的不饱和聚酯树脂；b) HUPR1 refers to the unsaturated polyester resin synthesized with diethylene glycol as diol;
c)HUPR2指以2-甲基-1,3-丙二醇为二元醇合成的不饱和聚酯树脂；c) HUPR2 refers to the unsaturated polyester resin synthesized with 2-methyl-1,3-propanediol as diol;
d)PAPI指多苯基多亚甲基多异氰酸酯d) PAPI refers to polyphenyl polymethylene polyisocyanate
e)MEKP为过氧化甲乙酮的邻苯二甲酸二甲酯溶液e) MEKP is a dimethyl phthalate solution of methyl ethyl ketone peroxide
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| WO2006109432A1 (en) * | 2005-03-30 | 2006-10-19 | Mitsui Chemicals Polyurethanes, Inc. | Two-component curable aqueous urethane-alkyd resin composition and use thereof |
| CN103396525A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | Unsaturated polyester resin for high-impact-resistance car bumper |
| CN103665311B (en) * | 2013-08-22 | 2016-04-13 | 常州大学 | A kind of dibasic alcohol preparation method of modified polyurethane/unsaturated polyester resin |
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| EP0011216A1 (en) * | 1978-11-08 | 1980-05-28 | Hans-Joachim Dr. Kiessling | Hardenable masses, process for the production of shaped articles therefrom and their utilization |
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| GB1182423A (en) * | 1966-06-16 | 1970-02-25 | Tercol Ltd | Improvements relating to Polymer Compositions |
| EP0011216A1 (en) * | 1978-11-08 | 1980-05-28 | Hans-Joachim Dr. Kiessling | Hardenable masses, process for the production of shaped articles therefrom and their utilization |
| JPS60146235A (en) * | 1984-01-11 | 1985-08-01 | Toray Ind Inc | Photosensitive resin for printing plate |
| JPH02189323A (en) * | 1989-01-18 | 1990-07-25 | Arakawa Chem Ind Co Ltd | Photocurable resin composition |
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