CN112920334B - Low-shrinkage unsaturated polyester resin and preparation method thereof - Google Patents
Low-shrinkage unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN112920334B CN112920334B CN202110338070.8A CN202110338070A CN112920334B CN 112920334 B CN112920334 B CN 112920334B CN 202110338070 A CN202110338070 A CN 202110338070A CN 112920334 B CN112920334 B CN 112920334B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
- C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
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Abstract
The invention provides a low-shrinkage unsaturated polyester resin and a preparation method thereof. The low-shrinkage unsaturated polyester resin is prepared by the following steps: reacting saturated dihydric alcohol with saturated dibasic acid (anhydride) to obtain double-end hydroxyl linear polyester; reacting double-end hydroxyl linear polyester with diisocyanate to obtain double-end isocyanate block copolymer; reacting double-end isocyanic acid radical block copolymer with hydroxyl acrylate to obtain a resin base material; mixing the resin base material with a crosslinking monomer to obtain low-shrinkage unsaturated polyester resin; wherein the molar ratio of the saturated dihydric alcohol to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of diisocyanate to saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the hydroxy acrylate to the saturated dibasic acid (anhydride) is (2-5): 1. The invention also provides a preparation method of the low-shrinkage unsaturated polyester resin, and the preparation method can efficiently and simply obtain the low-shrinkage unsaturated polyester resin.
Description
Technical Field
The invention relates to a low-shrinkage unsaturated polyester resin and a preparation method thereof, belonging to the field of high polymer materials.
Background
Unsaturated polyester resin molecular structure and crosslinking monomer contain unsaturated carbon-carbon double bond (-C-), and during crosslinking and curing, the unsaturated carbon-carbon double bond (-C-) is changed into carbon-carbon single bond (-C-C-), and the unsaturated polyester resin is shrunk after crosslinking and curing due to the reduction of occupied volume and the reduction of free volume caused by the reduction of molecular thermal motion. The linear shrinkage rate of the general unsaturated polyester resin is 2.0-2.5%, the volume shrinkage rate is as high as 8-10%, and the application of the general unsaturated polyester resin in occasions such as resin concrete castings, mortar terraces, large glass fiber reinforced plastic parts and the like is greatly limited.
In the prior art, in order to reduce the volume shrinkage of the unsaturated polyester resin, a low shrinkage agent can be added into a crosslinking curing system of the unsaturated polyester resin, but the low shrinkage agent does not participate in crosslinking curing and has high viscosity, so that the defects of poor manufacturability, low mechanical property of resin products and the like of the unsaturated polyester resin are easily caused.
How to reduce the shrinkage rate of unsaturated polyester resin in the cross-linking and curing process and expand the application range of the unsaturated polyester resin is a technical problem to be solved in the field of unsaturated polyester resin.
Disclosure of Invention
The invention provides a low-shrinkage unsaturated polyester resin, which reduces the content of unsaturated carbon-carbon double bonds in the unsaturated polyester resin by designing the types of raw materials for synthesizing the unsaturated polyester resin and the amount of each raw material, so that the curing shrinkage rate of the unsaturated polyester resin is small.
The invention also provides a preparation method of the low-shrinkage unsaturated polyester resin, and the low-shrinkage unsaturated polyester resin can be efficiently, simply and conveniently obtained by the preparation method.
The invention provides a low-shrinkage unsaturated polyester resin, which is prepared by a method comprising the following steps:
reacting saturated dihydric alcohol with saturated dibasic acid (anhydride) to obtain double-end hydroxyl linear polyester;
reacting the double-end hydroxyl linear polyester with diisocyanate to obtain a double-end isocyanate block copolymer;
reacting the double-end isocyanate block copolymer with hydroxyl acrylate to obtain the resin base material;
mixing the resin base material with a crosslinking monomer to obtain the low-shrinkage unsaturated polyester resin;
wherein the molar ratio of the saturated dihydric alcohol to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the diisocyanate to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the hydroxyl acrylic ester to the saturated dibasic acid (anhydride) is (2-5): 1.
The low shrinkage unsaturated polyester resin as described above, wherein the saturated diol is reacted with the saturated diacid (anhydride) to obtain the hydroxyl terminated linear polyester, comprising:
stirring saturated dihydric alcohol at 160 ℃, adding saturated dibasic acid (anhydride) until the saturated dibasic acid (anhydride) is dissolved, heating to 170-180 ℃, controlling the temperature of a distillation head to be lower than 103 ℃, and stopping reaction until the acid value reaches 20-30mgKOH to obtain the double-end hydroxyl linear polyester.
The low shrinkage unsaturated polyester resin as described above, wherein said reacting said hydroxyl-terminated linear polyester with a diisocyanate to obtain an isocyanate-terminated block copolymer, comprises:
at 70-80 ℃, sequentially adding diisocyanate and a catalyst 1 into the double-end hydroxyl linear polyester for reaction, and stopping the reaction when the isocyanate value reaches 0.025-0.028 to obtain the double-end isocyanate group block copolymer;
wherein the mass of the catalyst 1 is 0.10-0.30% of the sum of the masses of the double-end hydroxyl linear polyester and the diisocyanate.
The low shrinkage unsaturated polyester resin as described above, wherein said reacting said double-ended isocyanate block copolymer with a hydroxy acrylate to obtain said resin base comprises:
sequentially adding hydroxyl acrylate and a catalyst 2 into the double-end isocyanate group block copolymer at 65-70 ℃ for reaction, and stopping the reaction when the isocyanate value is 0 to obtain the resin base material;
wherein the mass of the catalyst 2 is 0.05-0.22% of the sum of the mass of the double-end isocyanate block copolymer and the mass of the hydroxyl acrylate.
The unsaturated polyester resin with low shrinkage as described above, wherein the saturated dibasic acid (anhydride) is at least one of phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, and adipic anhydride.
The low shrinkage unsaturated polyester resin, wherein the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
The low shrinkage unsaturated polyester resin, wherein the hydroxy acrylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The low-shrinkage unsaturated polyester resin is characterized in that the cross-linking monomer is 5.0-10.0% by mass.
The low-shrinkage unsaturated polyester resin is characterized in that the content of unsaturated carbon-carbon double bonds in the low-shrinkage unsaturated polyester resin is 2-3 mol/kg.
The invention also provides a preparation method of the low-shrinkage unsaturated polyester resin, which is characterized by comprising the following steps of:
reacting saturated dihydric alcohol with saturated dibasic acid (anhydride) to obtain double-end hydroxyl linear polyester;
reacting the double-end hydroxyl linear polyester with diisocyanate to obtain a double-end isocyanate block copolymer;
the double-end isocyanate block copolymer reacts with hydroxyl acrylate to obtain the resin base material;
mixing the resin base material with a crosslinking monomer to obtain the low-shrinkage unsaturated polyester resin;
wherein the molar ratio of the saturated dihydric alcohol to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the diisocyanate to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the hydroxyl acrylic ester to the saturated dibasic acid (anhydride) is 2-5: 1.
On one hand, the low-shrinkage unsaturated polyester resin is obtained by introducing supersaturated dibasic acid (anhydride), saturated dihydric alcohol, diisocyanate and hydroxyl acrylate into a resin base material to react, so that the content of unsaturated carbon-carbon double bonds in the resin base material is greatly reduced; on the other hand, the resin base material has low molecular weight and low content of unsaturated carbon-carbon double bonds, so that the dosage of the crosslinking monomer is low, and the content of the unsaturated carbon-carbon double bonds in the low-shrinkage unsaturated polyester resin is further reduced; therefore, the low-shrinkage unsaturated polyester resin has low content of unsaturated carbon-carbon double bonds, so that after the initiator is added into the low-shrinkage unsaturated polyester resin for crosslinking and curing, the curing shrinkage in the crosslinking and curing process is effectively inhibited, and particularly, the linear shrinkage of a casting body obtained after crosslinking and curing is controlled to be 0.2-0.7%.
In addition, the low shrinkage unsaturated polyester resin has low curing shrinkage, so that a low shrinkage agent is not required to be added in the curing process, and the problems of resin viscosity increase and poor manufacturability caused by the addition of the low shrinkage agent can be avoided.
It is worth mentioning that the low-shrinkage unsaturated polyester resin has small molecular weight, low viscosity and good fluidity, and can effectively discharge air bubbles in the using process, thereby reducing the defects of the cured product of the unsaturated polyester resin and being beneficial to improving the performance of the cured product of the unsaturated polyester resin. In addition, the low-shrinkage unsaturated polyester resin has low viscosity, and is more favorable for increasing the consumption of low-cost materials in products, thereby reducing the cost of the unsaturated polyester resin products.
The preparation method of the low-shrinkage unsaturated polyester resin has simple process, easy control of preparation process parameters and no need of the assistance of large-scale instruments and equipment, and the preparation method of the low-shrinkage unsaturated polyester resin has continuous process, does not need the procedures of purification and the like, has high yield of the unsaturated polyester resin, is suitable for large-scale quantitative production of the unsaturated polyester resin, and has extremely high popularization prospect.
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FIG. 1 is a schematic diagram of a process for preparing a low shrinkage unsaturated polyester resin according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a low-shrinkage unsaturated polyester resin, which is prepared by a method comprising the following steps:
s101: reacting saturated dihydric alcohol with saturated dibasic acid (anhydride) to obtain double-end hydroxyl linear polyester;
s102: reacting double-end hydroxyl linear polyester with diisocyanate to obtain double-end isocyanate block copolymer;
s103: reacting double-end isocyanic acid radical block copolymer with hydroxyl acrylate to obtain a resin base material;
s104: mixing the resin base material with a crosslinking monomer to obtain low-shrinkage unsaturated polyester resin;
wherein the molar ratio of the saturated dihydric alcohol to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the diisocyanate to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the hydroxyl acrylic ester to the saturated dibasic acid (anhydride) is (2-5): 1.
FIG. 1 is a schematic diagram of a process for preparing a low shrinkage unsaturated polyester resin according to an embodiment of the present invention.
In the present invention, saturated diols refer to alcohols having two terminal hydroxyl groups (-OH) and containing no carbon-carbon double bond (-C ═ C-) or carbon-carbon triple bond (-C ≡ C-) in the molecular structure; in the present invention, a saturated dibasic acid refers to an acid having two carboxyl groups (-COOH) and containing no carbon-carbon double bond (-C ═ C-) or carbon-carbon triple bond (-C ≡ C-) in its molecular structure; saturated dibasic acid anhydrides are acid anhydrides having one acid anhydride structure (-CO-O-CO-) without having a carbon-carbon double bond (-C-) or a carbon-carbon triple bond (-C ≡ C-) in the molecular structure; in the present invention, diisocyanate refers to an ester compound containing two isocyanate groups (-N ═ C ═ O) in the molecular structure; the hydroxyl acrylate in the invention refers to an acrylate compound containing one hydroxyl (-OH) in the molecular structure.
In the invention, the resin base material can be crosslinked and cured with the crosslinking monomer, thereby being beneficial to obtaining a cured low-shrinkage unsaturated polyester resin casting body. It is understood that, the resin binder and the crosslinking monomer both include unsaturated carbon-carbon double bonds, and during the crosslinking and curing process of the low shrinkage unsaturated polyester resin, the following reaction occurs in the low shrinkage unsaturated polyester resin: under the action of an initiator, unsaturated carbon-carbon double bonds of the resin base material and unsaturated carbon-carbon double bonds of the crosslinking monomer are subjected to crosslinking reaction, unsaturated carbon-carbon double bonds in the resin base material are subjected to crosslinking reaction, and unsaturated carbon-carbon double bonds in the crosslinking monomer are crosslinked, so that the low-shrinkage unsaturated polyester resin is cured, and is converted into an insoluble and infusible solid from a polymer solution.
The crosslinking monomer is not limited as long as it can crosslink and cure with the resin base, and in some embodiments of the invention, the crosslinking monomer may be at least one of styrene, vinyl toluene, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and lauryl methacrylate.
S101, each mole of saturated dibasic alcohol contains 2mol of hydroxyl (-OH), each mole of saturated dibasic acid contains 2mol of carboxyl (-COOH) or each mole of saturated dibasic acid anhydride contains 1mol of acid anhydride structure (-CO-O-CO-). Therefore, when saturated dihydric alcohol and saturated dibasic acid with the molar ratio of 2:1 are reacted, the mass ratio of hydroxyl (-OH) to carboxyl (-COOH) in the reaction system is 2:1, the hydroxyl (-OH) and the carboxyl (-COOH) are esterified according to the molar ratio of 1:1, each mol of saturated dihydric alcohol participates in the reaction, and 2mol of hydroxyl (-OH) are remained after the reaction is completed; or the mass ratio of hydroxyl (-OH) to anhydride (-CO-O-CO-) in the reaction system is 4:1, and the hydroxyl (-OH) and the anhydride (-CO-O-CO-) are esterified according to the molar ratio of 2: 1; therefore, the hydroxyl group (-OH) in the reaction system is excessive, and the double-terminal hydroxyl group linear polyester can be obtained.
In S102, each mole of the double hydroxyl group-terminated linear polyester contains 2 moles of hydroxyl group (-OH) at both ends of the molecular structure and 2 moles of isocyanate group (-N ═ C ═ O) per mole of the molecular structure of diisocyanate, and therefore, when the double hydroxyl group-terminated linear polyester having a molar ratio of 1:2 is reacted with diisocyanate, the hydroxyl group (-OH) and the isocyanate group (-N ═ C ═ O) are esterified in a molar ratio of 1:1 to obtain an isocyanate group (-N-CO-O-), the remaining 2 moles of the isocyanate group (-N ═ C ═ O), and the isocyanate group (-N ═ C ═ O) is excessive, and thus a double isocyanate group block copolymer can be obtained.
In S103, each mole of the molecular structure of the double-ended isocyanate block copolymer contains 2 moles of isocyanate group (-N ═ C ═ O), and thus, when the double-ended isocyanate block copolymer having a molar ratio of 1 (2-5) is reacted with a hydroxy acrylate, the isocyanate group (-N ═ C ═ O) and the hydroxy group (-OH) undergo an esterification reaction in a molar ratio of 1:1, and unsaturated carbon-carbon double bonds in the hydroxy acrylate are introduced, so that the molecular structure of the obtained resin base material includes the unsaturated carbon-carbon double bonds, and the hydroxy acrylate not involved in the reaction is dissociated in the resin base material.
The method comprises the steps of firstly obtaining double-end hydroxyl linear polyester by using saturated dihydric alcohol and saturated dibasic acid (anhydride) with a molar ratio of 2:1, then introducing isocyanate (-N ═ C ═ O) into the double-end hydroxyl linear polyester by enabling diisocyanate and the double-end hydroxyl linear polyester to react according to the molar ratio of 2:1 to obtain double-end isocyanate block copolymer, and then introducing unsaturated carbon-carbon double bonds into a resin base material by enabling hydroxyl acrylate and the double-end isocyanate block copolymer to react according to the ratio of (2-5): 1. The invention uses saturated dibasic acid (anhydride), saturated dibasic alcohol, diisocyanate and hydroxyl acrylate as raw materials of the synthetic resin base material, and only the hydroxyl acrylate in the raw materials contains unsaturated carbon-carbon double bonds, so that the content of the unsaturated carbon-carbon double bonds in the resin base material is greatly reduced, and the content of the unsaturated carbon-carbon double bonds in the low-shrinkage unsaturated polyester resin is reduced; moreover, the low-shrinkage unsaturated polyester resin obtained by the technical scheme of the invention has low molecular weight and low content of unsaturated carbon-carbon double bonds, so that the dosage of the crosslinking monomer is small, and the content of the unsaturated carbon-carbon double bonds brought by the crosslinking monomer is low, thereby further reducing the content of the carbon-carbon double bonds in the low-shrinkage unsaturated polyester resin; therefore, the low-shrinkage unsaturated polyester resin has low carbon-carbon double bond content and low curing shrinkage rate in the cross-linking and curing process.
The reaction conditions for obtaining the double-end hydroxyl linear polyester by the reaction of the saturated dihydric alcohol and the saturated dibasic acid (anhydride) are not strictly limited. In some embodiments of the invention, a saturated diol is reacted with a saturated diacid (anhydride) to provide a double hydroxyl terminated linear polyester comprising:
stirring saturated dihydric alcohol at 160 ℃, adding saturated dibasic acid (anhydride) until the saturated dibasic acid (anhydride) is dissolved, heating to 170-180 ℃, controlling the temperature of a distillation head to be lower than 103 ℃, and stopping reaction until the acid value reaches 20-30mgKOH to obtain the double-end hydroxyl linear polyester.
In the present invention, the acid value means the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of a substance. The acid value during the reaction of the saturated diol with the saturated dibasic acid (anhydride) may reflect the degree of progress of the esterification reaction. In the present invention, the molar ratio of the saturated diol to the saturated dibasic acid (anhydride) is 2:1, and the reaction of the saturated diol with the saturated dibasic acid (anhydride) is substantially completed when the acid value is in the range of 20 to 30 mgKOH. In the specific implementation process, the acid value can be obtained by a method for testing the hydroxyl value of the low-shrinkage unsaturated polyester resin defined in GB/T7193-2008 low-shrinkage unsaturated polyester resin test.
The esterification reaction of the saturated dihydric alcohol and the saturated dibasic acid (anhydride) is carried out under the reaction conditions, so that the saturated dihydric alcohol and the saturated dibasic acid (anhydride) in a reaction system can be effectively prevented from cyclization in the reaction process, the saturated dihydric alcohol and the saturated dibasic acid (anhydride) are promoted to obtain the double-end hydroxyl linear polyester, and the high-yield double-end hydroxyl linear polyester can be obtained without carrying out operations such as purification on a reaction product.
The inventor finds that the temperature rise process of raising the temperature to 170-180 ℃ after the saturated dibasic acid is dissolved has influence on the yield of the double-end hydroxyl linear polyester in the research process. In some embodiments of the invention, the ramp rate is 1-2 deg.C/min. The temperature is increased to 170-180 ℃ at the temperature-increasing rate of 1-2 ℃/min, so that the polymerization of saturated dibasic acid and saturated dihydric alcohol can be promoted to generate the double-end hydroxyl linear polyester, and the yield of the double-end hydroxyl linear polyester is favorably improved.
In some embodiments of the present invention, a double hydroxyl-terminated linear polyester is reacted with a diisocyanate to provide a double isocyanate-terminated block copolymer comprising:
at 70-80 ℃, sequentially adding diisocyanate and a catalyst 1 into double-end hydroxyl linear polyester for reaction, and stopping the reaction when the isocyanate value reaches 0.025-0.028 to obtain double-end isocyanate block copolymer;
wherein the mass of the catalyst 1 is 0.10-0.30% of the sum of the masses of the double-end hydroxyl linear polyester and the diisocyanate.
In the present invention, the isocyanate group value refers to the ratio of the mass of isocyanate group (-NCO) in the material to the total mass of the material, and can be obtained by the test method defined in ASTM D5155-2007 standard test method for polyurethane raw materials, measurement of isocyanate content in aromatic isocyanate (method a). In the reaction process of the double-hydroxyl linear polyester and the diisocyanate, the isocyanate value can reflect the degree of the reaction. In the invention, the molar ratio of the double-end hydroxyl linear polyester to the diisocyanate is 1:2, the reaction is stopped when the isocyanate value in the reaction system reaches 0.025-0.028, and the hydroxyl (-OH) in the reaction system is basically completely reacted.
The catalyst 1 is not particularly limited in the present invention as long as it can catalyze the reaction of the double hydroxyl-terminated linear polyester with the diisocyanate. In some embodiments of the invention, catalyst 1 may be at least one of N, N' -dimethylpiperazine, N-methyloxymorpholine, N-ethylmorpholine, dibutyltin dilaurate.
According to the invention, the reaction of the double-hydroxyl-end linear polyester and the diisocyanate is carried out under the reaction conditions, so that hydroxyl (-OH) in the double-hydroxyl-end linear polyester can be reacted completely, the ring forming reaction of the double-hydroxyl-end linear polyester and the diisocyanate is avoided, and the double-end isocyanate block copolymer can be obtained efficiently.
The invention does not strictly limit the reaction conditions of the double-end isocyanate group block copolymer and the hydroxyl acrylate, as long as the reaction of the double-end isocyanate group block copolymer and the hydroxyl acrylate can be realized to obtain the resin base material. In some embodiments of the invention, a double-ended isocyanate block copolymer is reacted with a hydroxy acrylate to provide a resinous binder comprising:
sequentially adding hydroxyl acrylate and a catalyst 2 into the double-end isocyanate group block copolymer at 65-70 ℃ for reaction, and stopping the reaction when the isocyanate group value is 0 to obtain the resin base material;
wherein the mass of the catalyst 2 is 0.05-0.22% of the sum of the mass of the double-end isocyanate-terminated block copolymer and the mass of the hydroxyl acrylate.
The catalyst 2 is not strictly limited in the present invention as long as it can catalyze the reaction of the double-ended isocyanato block copolymer with the hydroxyacrylate. In some embodiments of the invention, catalyst 2 is at least one of triethylenediamine, dimethylethanolamine, N' -dimethylpiperazine, and dimorpholinoether.
Through the reaction conditions, the reaction of the isocyanic acid radical (-N ═ C ═ O) in the double-end isocyanic acid radical block copolymer and the hydroxyl (-OH) in the hydroxyl acrylate can be realized, and the unsaturated carbon-carbon double bond in the hydroxyl acrylate is introduced into the resin base material.
The inventor finds in the research process that the curing shrinkage of the unsaturated polyester resin can be further reduced by controlling the molar ratio of the hydroxy acrylate to the saturated dibasic acid (anhydride).
In some embodiments of the present invention, the molar ratio of the hydroxy acrylate to the saturated dibasic acid (anhydride) is 2:1, wherein the amount of hydroxyl in the hydroxy acrylate is sufficient to complete the isocyanate reaction in the double-ended isocyanate block copolymer, unsaturated carbon-carbon double bonds are introduced at a lower feed rate of the hydroxy acrylate, and the curing shrinkage of the unsaturated polyester resin is further reduced by reducing the amount of unreacted hydroxy acrylate in the system, so that the content of unsaturated carbon-carbon double bonds in the resin base material is further reduced.
The saturated diol is not particularly limited in the present invention, and for example, the saturated diol may be at least one of ethylene glycol, 1.2-propylene glycol, 1.3-propylene glycol, methylpropylene glycol, diethylene glycol, dipropylene glycol, and neopentyl glycol.
The position of the hydroxyl group (-OH) in the saturated diol in the carbon chain structure is not strictly limited in the present invention, for example, the hydroxyl group may be at both ends of the carbon chain or in the middle of the carbon chain. In the specific implementation process, in order to reduce the steric hindrance when the hydroxyl (-OH) reacts with the carboxyl (-COOH) group, and prevent the cyclization of two hydroxyl (-OH) groups on the same carbon chain with two carboxyl (-COOH) groups or an anhydride structure (-CO-O-CO-) on the same carbon chain of the saturated dibasic acid (anhydride), the saturated dibasic alcohol with the hydroxyl groups at two ends of the carbon chain can be selected.
The saturated dibasic acid (anhydride) is not strictly limited by the present invention, and in some embodiments of the present invention, the saturated dibasic acid (anhydride) is at least one of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, and adipic anhydride.
The diisocyanate is not strictly limited in the present invention, and in some embodiments of the present invention, the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
The present invention is not limited to the hydroxy acrylic acid ester, and in some embodiments of the present invention, the hydroxy acrylic acid ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
The crosslinking monomer is not particularly limited in the present invention, so long as the crosslinking monomer can be cured and crosslinked with the resin base material. In some embodiments of the invention, the crosslinking monomer is at least one of styrene, vinyl toluene, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate.
In order to improve the stability of the low-shrinkage unsaturated polyester resin, prevent the resin base material and the crosslinking monomer from being crosslinked in the standing process and prolong the storage time of the low-shrinkage unsaturated polyester resin, in some embodiments of the invention, the low-shrinkage unsaturated polyester resin further comprises a polymerization inhibitor, and the mass of the polymerization inhibitor is 0.005-0.025% of that of the resin base material.
In the specific implementation process, after the resin base material is obtained, the polymerization inhibitor is added into the resin base material, and then the resin base material containing the polymerization inhibitor is mixed with the crosslinking monomer to obtain the low-shrinkage unsaturated polyester resin.
The polymerization inhibitor of the present invention is not particularly limited, and for example, the polymerization inhibitor may be at least one of hydroquinone, benzoquinone, p-t-butylcatechol, methylhydroquinone, di-t-butyl-p-cresol, 2-t-butylhydroquinone, and p-hydroxyanisole.
In some embodiments of the present invention, the low shrinkage unsaturated polyester resin comprises 5.0 to 10.0% by mass of the crosslinking monomer.
In the use process of the low-shrinkage unsaturated polyester resin, the crosslinking monomer in the low-shrinkage unsaturated polyester resin can not only crosslink with the resin base material, but also play a role in adjusting the viscosity of the low-shrinkage unsaturated polyester resin.
According to the invention, different raw materials, reaction conditions among the raw materials and the addition amount of the hydroxyl acrylate are selected in the unsaturated polyester resin synthesis process, so that the content of unsaturated carbon-carbon double bonds in the resin base material is low, and the molecular weight of the resin base material is small, therefore, when the mass percentage of the crosslinking monomer in the unsaturated polyester resin is 5.0-10.0%, the viscosity of the unsaturated polyester resin can reach 200-400 mPa.s, the unsaturated polyester resin has good fluidity and good manufacturability in use, meanwhile, the resin base material and the crosslinking monomer in the unsaturated polyester resin can be effectively crosslinked, and the cured unsaturated polyester resin has excellent performance.
In some embodiments of the present invention, the unsaturated polyester resin with low shrinkage has an unsaturated carbon-carbon double bond content of 2 to 3 mol/kg.
In the invention, the content of unsaturated carbon-carbon double bonds can be obtained by a theoretical calculation method, and specifically, the content of the unsaturated carbon-carbon double bonds in the unsaturated polyester resin is the ratio of the sum of the amounts of substances of the unsaturated carbon-carbon double bonds in the added raw materials to the mass of the unsaturated polyester resin. In the present invention, the content of unsaturated carbon-carbon double bonds in the unsaturated polyester resin is mainly introduced into the resin base material from the hydroxy acrylate, and therefore, the amount of the substance having unsaturated carbon-carbon double bonds in the unsaturated polyester resin depends on the amount of the substance having hydroxy acrylate. In the specific implementation process, the quality of the unsaturated polyester resin can be regulated and controlled through the raw material input quality, and the content of unsaturated carbon-carbon double bonds in the unsaturated polyester resin can be in the range by matching with the control of the amount of the hydroxyl acrylate substance.
The second aspect of the present invention provides a method for preparing the low shrinkage unsaturated polyester resin, comprising the following steps:
reacting saturated dihydric alcohol with saturated dibasic acid (anhydride) to obtain double-end hydroxyl linear polyester;
reacting double-end hydroxyl linear polyester with diisocyanate to obtain double-end isocyanate block copolymer;
reacting double-end isocyanic acid radical block copolymer with hydroxyl acrylate to obtain resin base material;
mixing the resin base material with a crosslinking monomer to obtain low-shrinkage unsaturated polyester resin;
wherein the molar ratio of the saturated dihydric alcohol to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of diisocyanate to saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the hydroxyl acrylic ester to the saturated dibasic acid (anhydride) is 2-5: 1.
The preparation method of the low-shrinkage unsaturated polyester resin can effectively obtain the low-shrinkage unsaturated polyester resin, the preparation process is simple and easy to control, and the yield of the unsaturated polyester resin is high.
Hereinafter, the low shrinkage unsaturated polyester resin and the method for preparing the low shrinkage unsaturated polyester resin according to the present invention will be described in detail by way of specific examples. In the following examples, each raw material was commercially available.
Example 1
1. Putting 150kg of 1.3-propylene glycol into a reaction kettle, heating the reaction kettle to 160 ℃ and keeping the temperature, stirring the propylene glycol, adding 165kg of phthalic acid into the reaction kettle until the phthalic acid is completely dissolved, heating the reaction kettle to 170 ℃ at the heating rate of 1-2 ℃/min, controlling the temperature of a distillation head to be lower than 103 ℃, and reducing the temperature of the reaction kettle to 80 ℃ until the acid value reaches 20-30mgKOH to obtain double-end hydroxyl linear polyester;
2. keeping the temperature of the reaction kettle at 70-80 ℃, sequentially adding 350kg of toluene diisocyanate and 1.1kg of dibutyltin dilaurate into the reaction kettle for reaction, and cooling the reaction kettle to 65-70 ℃ after the isocyanate value reaches 0.025-0.028 to obtain a double-end isocyanato group block copolymer;
3. keeping the temperature of the reaction kettle at 65-70 ℃, sequentially adding 280kg of hydroxyethyl methacrylate and 1.5kg of dimethylethanolamine into the reaction kettle for reaction, and cooling the reaction kettle to room temperature when the isocyanate value is 0 to obtain a resin base material;
4. and (3) sequentially adding 0.15kg of hydroquinone and 60kg of styrene into the reaction kettle, uniformly mixing, and stopping stirring to obtain the low-shrinkage unsaturated polyester resin.
Example 2
1. Putting 180kg of 2-methyl-1, 3-propylene glycol into a reaction kettle, heating the reaction kettle to 160 ℃ and keeping the temperature, stirring the methyl propylene glycol, adding 165kg of isophthalic acid into the reaction kettle until the isophthalic acid is completely dissolved, heating the reaction kettle to 170 ℃ at the heating rate of 1-2 ℃/min, controlling the temperature of a distillation head to be lower than 103 ℃, and reducing the temperature of the reaction kettle to 80 ℃ until the acid value reaches 20-30mgKOH to obtain the double-end hydroxyl linear polyester;
2. keeping the temperature of the reaction kettle at 70-80 ℃, sequentially adding 500kg of 4,4' -diphenylmethane diisocyanate and 1.2kg of dibutyltin dilaurate into the reaction kettle for reaction, and cooling the reaction kettle to 65-70 ℃ after the isocyanate value reaches 0.025-0.028 to obtain a double-end isocyanate group block copolymer;
3. keeping the temperature of the reaction kettle at 65-70 ℃, sequentially adding 300kg of hydroxypropyl methacrylate and 1.2kg of N, N' -dimethylpiperazine into the reaction kettle for reaction, and cooling the reaction kettle to room temperature when the isocyanate value is 0 to obtain a resin base material;
4. 0.12kg of p-tert-butylcatechol and 100kg of styrene are sequentially added into the reaction kettle, and the mixture is uniformly mixed and then is stopped stirring to obtain the low-shrinkage unsaturated polyester resin.
Example 3
1. 267kg of dipropylene glycol is put into a reaction kettle, the temperature of the reaction kettle is raised to 160 ℃ and kept, the dipropylene glycol is stirred and 165kg of terephthalic acid is added into the reaction kettle until the terephthalic acid is completely dissolved, then the temperature of the reaction kettle is raised to 170 ℃ at the temperature raising rate of 1-2 ℃/min, the temperature of a distillation head is controlled to be lower than 103 ℃, the temperature of the reaction kettle is lowered to 80 ℃ until the acid value reaches 20-30mgKOH, and the double-end hydroxyl linear polyester is obtained;
2. keeping the temperature of the reaction kettle at 70-80 ℃, sequentially adding 450kg of isophorone diisocyanate and 1.5kg of N-ethyl morpholine into the reaction kettle for reaction, and cooling the reaction kettle to 65-70 ℃ after the isocyanate value reaches 0.025-0.028 to obtain a double-end isocyanate group block copolymer;
3. keeping the temperature of the reaction kettle at 65-70 ℃, sequentially adding 232kg of hydroxyethyl acrylate and 1.6kg of dimorpholinoethyl ether into the reaction kettle for reaction, and cooling the reaction kettle to room temperature when the isocyanate value is 0 to obtain a resin base material;
4. 0.16kg of ditert-butyl-p-cresol and 80kg of styrene are sequentially added into a reaction kettle, and stirring is stopped after uniform mixing, so that the low-shrinkage unsaturated polyester resin is obtained.
Example 4
1. Putting 220kg of diethylene glycol into a reaction kettle, heating the reaction kettle to 160 ℃ and keeping the temperature, stirring the dipropylene glycol, adding 150kg of adipic acid into the reaction kettle until the adipic acid is completely dissolved, heating the reaction kettle to 170 ℃ at the heating rate of 1-2 ℃/min, controlling the temperature of a distillation head to be lower than 103 ℃, and reducing the temperature of the reaction kettle to 80 ℃ until the acid value reaches 20-30mgKOH to obtain double-end hydroxyl linear polyester;
2. keeping the temperature of the reaction kettle at 70-80 ℃, sequentially adding 350kg of toluene diisocyanate and 1.6kg of N, N' -dimethyl piperazine into the reaction kettle for reaction, and cooling the reaction kettle to 65-70 ℃ after the isocyanate value reaches 0.025-0.028 to obtain a double-end isocyanato group block copolymer;
3. keeping the temperature of the reaction kettle at 65-70 ℃, sequentially adding 270kg of hydroxyethyl methacrylate and 1.6kg of dimethylethanolamine into the reaction kettle for reaction, and cooling the reaction kettle to room temperature when the isocyanate value is 0 to obtain a resin base material;
4. and (3) sequentially adding 0.1kg of 2-tert-butylhydroquinone and 90kg of styrene into the reaction kettle, uniformly mixing, and stopping stirring to obtain the low-shrinkage unsaturated polyester resin.
Example 5
1. Putting 150kg of 1.3-propylene glycol into a reaction kettle, heating the reaction kettle to 160 ℃ and keeping the temperature, stirring the propylene glycol, adding 165kg of phthalic acid into the reaction kettle until the phthalic acid is completely dissolved, heating the reaction kettle to 170 ℃ at the heating rate of 1-2 ℃/min, controlling the temperature of a distillation head to be lower than 103 ℃, and reducing the temperature of the reaction kettle to 80 ℃ until the acid value reaches 20-30mgKOH to obtain double-end hydroxyl linear polyester;
2. keeping the temperature of the reaction kettle at 70-80 ℃, sequentially adding 350kg of toluene diisocyanate and 1.1kg of dibutyltin dilaurate into the reaction kettle for reaction, and cooling the reaction kettle to 65-70 ℃ after the isocyanate value reaches 0.025-0.028 to obtain a double-end isocyanato block copolymer;
3. keeping the temperature of the reaction kettle at 65-70 ℃, sequentially adding 550kg of hydroxyethyl methacrylate and 1.5kg of dimethylethanolamine into the reaction kettle for reaction, and cooling the reaction kettle to room temperature when the isocyanate value is 0 to obtain a resin base material;
4. and (3) sequentially adding 0.17kg of hydroquinone and 70kg of styrene into the reaction kettle, uniformly mixing, and stopping stirring to obtain the low-shrinkage unsaturated polyester resin.
Comparative example 1
1. Putting 150kg of 1, 3-propylene glycol into a reaction kettle, heating the reaction kettle to 160 ℃ and keeping the temperature, stirring the propylene glycol, adding 98kg of maleic anhydride into the reaction kettle until the maleic anhydride is completely dissolved, heating the reaction kettle to 170 ℃ at the heating rate of 1-2 ℃/min, controlling the temperature of a distillation head to be lower than 103 ℃, and reducing the temperature of the reaction kettle to 80 ℃ until the acid value reaches 20-30mgKOH to obtain the double-end hydroxyl linear polyester;
2. keeping the temperature of the reaction kettle at 70-80 ℃, sequentially adding 350kg of toluene diisocyanate and 1.1kg of dibutyltin dilaurate into the reaction kettle for reaction, and cooling the reaction kettle to 65-70 ℃ after the isocyanate value reaches 0.025-0.028 to obtain a double-end isocyanato block copolymer;
3. keeping the reaction kettle at 65-70 ℃, sequentially adding 280kg of hydroxyethyl methacrylate and 1.5kg of dimethylethanolamine into the reaction kettle for reaction, and cooling the reaction kettle to room temperature when the isocyanate value is 0 to obtain a resin base material;
4. and (3) sequentially adding 0.15kg of hydroquinone and 60kg of styrene into the reaction kettle, uniformly mixing, and stopping stirring to obtain the unsaturated polyester resin.
Comparative example 2
1. Putting 228Kg of 1, 3-propylene glycol into a reaction kettle, heating the reaction kettle to 160 ℃ and keeping the temperature, stirring the propylene glycol, adding 166Kg of phthalic acid and 196Kg of maleic anhydride into the reaction kettle until the phthalic acid and the maleic anhydride are completely dissolved, heating the reaction kettle to 198 ℃ at the heating rate of 2-3 ℃/min, controlling the temperature of a distillation head to be lower than 103 ℃, and obtaining an unsaturated polyester resin prepolymer until the acid value reaches 20-30 mgKOH;
2. adding 1.0Kg of hydroquinone into the unsaturated polyester resin prepolymer, and cooling to 150 ℃;
3. and adding 400Kg of styrene into the diluting kettle, and adding a prepolymer containing a polymerization inhibitor into the diluting kettle to obtain the unsaturated polyester resin.
In the above examples and comparative examples, the acid value and isocyanate value were measured by the following methods: taking the mixture in the reaction kettle, obtaining the acid value according to the test method defined in GB/T7193-2008 unsaturated polyester resin test method, and obtaining the isocyanate value according to the test method defined in ASTM D5155-2007 Standard test method for polyurethane raw materials (method A) for measuring the isocyanate content in aromatic isocyanate.
Test examples
The unsaturated polyester resins obtained in examples 1 to 5 and comparative examples 1 to 2 were tested for viscosity, relative molecular mass, and cure shrinkage; the unsaturated carbon-carbon double bond content of the unsaturated polyester resin was calculated and the results are shown in table 1.
1. Carbon-carbon double bond content: the ratio of the sum of the amount of the substance of the hydroxy acrylate and the amount of the substance of the crosslinking monomer in the raw materials to the total mass of the unsaturated polyester resin;
2. viscosity: the viscosity of the unsaturated polyester resin was measured at 25 ℃ using an NDJ-79 viscometer.
3. Curing shrinkage rate: weighing 1.5Kg of unsaturated polyester resin, adding 15g of cobalt iso-octoate solution (the mass concentration of cobalt iso-octoate is 1%) as an accelerator into the unsaturated polyester, uniformly stirring, then adding 18g of methyl ethyl ketone peroxide solution (the mass content of active oxygen is 9-10%) as an initiator into the unsaturated polyester, uniformly stirring, pouring into a steel die with the size of 1000mm multiplied by 50mm, curing for 24 hours at the temperature of 23 +/-2 ℃ to obtain an unsaturated polyester resin casting body, and testing the length of the unsaturated polyester resin casting body before and after curing; the curing shrinkage ratio (length of the unsaturated polyester resin cast body before curing-length of the unsaturated polyester resin cast body after curing)/length of the unsaturated polyester resin cast body before curing;
4. relative molecular mass: the molecular weight of the unsaturated polyester resin was measured using Gel Permeation Chromatography (GPC).
As can be seen from Table 1:
1. examples 1-5 compared to comparative examples 1-2, examples 1-5 had low unsaturated carbon-carbon double bond content and low shrinkage of the unsaturated polyester resin, and the viscosity of the unsaturated polyester resin was low due to the following reasons: the low-shrinkage unsaturated polyester resin is obtained by reacting saturated dibasic acid with saturated dihydric alcohol;
2. example 5 compared with example 1, the unsaturated polyester resin of the low shrinkage unsaturated polyester resin obtained in example 1 has a low content of unsaturated carbon-carbon double bonds and a low shrinkage ratio due to the following reasons: the molar ratio of the hydroxyl acrylate to the saturated dibasic acid (anhydride) in example 1 is 2:1, the molar ratio of the hydroxyl acrylate to the saturated dibasic acid (anhydride) in example 5 is 4:1, the amount of the hydroxyl in the hydroxyl acrylate added in example 1 is enough to ensure that the isocyanate in the double-ended isocyanate block copolymer is completely reacted, unsaturated carbon-carbon double bonds are introduced under lower charging of the hydroxyl acrylate, the amount of the hydroxyl acrylate which does not participate in the reaction in the system is reduced, the content of the unsaturated carbon-carbon double bonds in the resin base material is further reduced, the content of the unsaturated carbon-carbon double bonds in the low-shrinkage unsaturated polyester resin is reduced, and the curing shrinkage rate of the low-shrinkage unsaturated polyester resin is further reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A low shrinkage unsaturated polyester resin, characterized in that it is prepared by a process comprising:
reacting saturated dihydric alcohol with saturated dibasic acid (anhydride) to obtain double-end hydroxyl linear polyester;
reacting the double-end hydroxyl linear polyester with diisocyanate to obtain a double-end isocyanate block copolymer;
reacting the double-end isocyanate block copolymer with hydroxyl acrylate to obtain the resin base material;
mixing the resin base material with a crosslinking monomer to obtain the low-shrinkage unsaturated polyester resin;
wherein the molar ratio of the saturated dihydric alcohol to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the diisocyanate to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the hydroxyl acrylic ester to the saturated dibasic acid (anhydride) is (2-5) to 1;
in the low-shrinkage unsaturated polyester resin, the mass percentage of the crosslinking monomer is 5.0-10.0%.
2. The low shrinkage unsaturated polyester resin of claim 1, wherein said reacting saturated diol with saturated diacid (anhydride) to obtain hydroxyl terminated linear polyester comprises:
stirring saturated dihydric alcohol at 160 ℃, adding saturated dibasic acid (anhydride) until the saturated dibasic acid (anhydride) is dissolved, heating to 170-180 ℃, controlling the temperature of a distillation head to be lower than 103 ℃, and stopping reaction until the acid value reaches 20-30mgKOH to obtain the double-end hydroxyl linear polyester.
3. The low profile unsaturated polyester resin according to claim 1 or 2, wherein said double hydroxyl-terminated linear polyester is reacted with a diisocyanate to obtain a double isocyanate-terminated block copolymer comprising:
at the temperature of 70-80 ℃, diisocyanate and a catalyst 1 are sequentially added into the double-end hydroxyl linear polyester for reaction, and the reaction is stopped when the isocyanate value reaches 0.025-0.028, so that the double-end isocyanate block copolymer is obtained;
wherein the mass of the catalyst 1 is 0.10-0.30% of the sum of the masses of the double-hydroxyl linear polyester and the diisocyanate.
4. The low shrinkage unsaturated polyester resin of claim 1 or 2, wherein said reacting said double-ended isocyanate block copolymer with a hydroxy acrylate to obtain said resin base comprises:
sequentially adding hydroxyl acrylate and a catalyst 2 into the double-end isocyanate group block copolymer at 65-70 ℃ for reaction, and stopping the reaction when the isocyanate value is 0 to obtain the resin base material;
wherein the mass of the catalyst 2 is 0.05-0.22% of the sum of the mass of the double-end isocyanate block copolymer and the mass of the hydroxyl acrylate.
5. The low shrinkage unsaturated polyester resin of claim 3, wherein said reacting said double end isocyanate block copolymer with a hydroxy acrylate to obtain said resin binder comprises:
sequentially adding hydroxyl acrylate and a catalyst 2 into the double-end isocyanate group block copolymer at 65-70 ℃ for reaction, and stopping the reaction when the isocyanate value is 0 to obtain the resin base material;
wherein the mass of the catalyst 2 is 0.05-0.22% of the sum of the mass of the double-end isocyanate block copolymer and the mass of the hydroxyl acrylate.
6. The low shrinkage unsaturated polyester resin according to claim 1, wherein the saturated dibasic acid (anhydride) is at least one of phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, and adipic anhydride.
7. The unsaturated polyester resin of claim 1, wherein the diisocyanate is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
8. The low shrinkage unsaturated polyester resin according to claim 1, wherein the hydroxy acrylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
9. The low shrinkage unsaturated polyester resin according to any one of claims 1, 2, 5 to 8, wherein the content of unsaturated carbon-carbon double bonds in the low shrinkage unsaturated polyester resin is 2 to 3 mol/kg.
10. A process for the preparation of a low shrinkage unsaturated polyester resin according to any of claims 1 to 9, comprising the steps of:
reacting saturated dihydric alcohol with saturated dibasic acid (anhydride) to obtain double-end hydroxyl linear polyester;
reacting the double-end hydroxyl linear polyester with diisocyanate to obtain a double-end isocyanate block copolymer;
the double-end isocyanate block copolymer reacts with hydroxyl acrylate to obtain the resin base material;
mixing the resin base material with a crosslinking monomer to obtain the low-shrinkage unsaturated polyester resin;
wherein the molar ratio of the saturated dihydric alcohol to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the diisocyanate to the saturated dibasic acid (anhydride) is 2: 1; the molar ratio of the hydroxyl acrylic ester to the saturated dibasic acid (anhydride) is 2-5: 1.
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| DE2114443A1 (en) * | 1970-03-26 | 1971-10-14 | Kansai Paint Co Ltd | Process for the production of polyester resin |
| CN102858824A (en) * | 2010-11-19 | 2013-01-02 | Dic株式会社 | Radical-curable resin composition, coating material and civil engineering building structure each using radical-curable resin composition, and method for constructing civil engineering building structure |
| 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 |
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| DE2114443A1 (en) * | 1970-03-26 | 1971-10-14 | Kansai Paint Co Ltd | Process for the production of polyester resin |
| CN102858824A (en) * | 2010-11-19 | 2013-01-02 | Dic株式会社 | Radical-curable resin composition, coating material and civil engineering building structure each using radical-curable resin composition, and method for constructing civil engineering building structure |
| 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 |
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