CN111647148A - Alicyclic structure ester polymer and compound, preparation method and application - Google Patents

Alicyclic structure ester polymer and compound, preparation method and application Download PDF

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CN111647148A
CN111647148A CN202010422257.1A CN202010422257A CN111647148A CN 111647148 A CN111647148 A CN 111647148A CN 202010422257 A CN202010422257 A CN 202010422257A CN 111647148 A CN111647148 A CN 111647148A
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ester polymer
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CN111647148B (en
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狄宁宇
虞希高
许坤
王文佳
程微
胡萧勇
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Zhejiang Bofei Electrical Co ltd
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    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
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Abstract

An alicyclic structure ester polymer is low-viscosity unsaturated polyester and comprises, by weight, 45-60 parts of alicyclic polyhydric alcohol, 0-15 parts of aliphatic polyhydric alcohol, 15-25 parts of unsaturated acid (anhydride), 10-30 parts of alicyclic polybasic acid (anhydride), 1-5 parts of pyrrole compound, 0.01-2 parts of solid acid catalyst, 0.01-0.3 part of polymerization inhibitor and 15-30 parts of cross-linking agent. The ester polymer and the resin-based active compound prepared from the ester polymer have the characteristics of low viscosity, humidity resistance, low volatility, high curing speed, high strength and the like, and can effectively improve the electrical performance and the curing strength of the product by introducing the solid acid catalyst and using the monofunctional group pyrrole compound as an end-capping agent.

Description

Alicyclic structure ester polymer and compound, preparation method and application
Technical Field
The present invention relates to an ester polymer, in particular to a low molecular weight ester polymer containing an alicyclic structure, and the preparation of an environment-friendly resin-based composite, and the application in a VPI process.
Background
Unsaturated polyester is a common one in thermosetting resins, and is an ester polymer containing active unsaturated double bonds, which is mainly generated by the polycondensation reaction of dibasic acid and dihydric alcohol.
The unsaturated polyester is generally solid and dissolved in a compound having an activated double bond, such as styrene, vinyl toluene, acrylic ester, methacrylic acid polyester, allyl ether or ester, and the like, to constitute a liquid unsaturated polyester resin. These low viscosity "reactive double bond compounds" serve to copolymerize and crosslink and reduce the viscosity of the unsaturated polyester and are commonly referred to as "crosslinkers" or "reactive diluents".
The most common unsaturated polyester cross-linking agents are styrene and vinyl toluene with a boiling point slightly higher than that of styrene, which have low viscosity, good diluting capability and copolymerization activity, but because styrene or vinyl toluene are easily volatile and have heavy odor, serious environmental protection problems and potential safety hazards are brought to resin synthesis and application enterprises.
The unsaturated polyester is a long-chain polymer with a molecular weight of 1,000-3,000, and is generally synthesized by an alcohol excess method, so that the terminal group is mainly hydroxyl. If the crosslinking agent with low volatility and high boiling point (above 250 ℃) is selected to completely replace styrene (vinyl toluene) and the like to dissolve unsaturated polyester, the environment-friendly unsaturated polyester resin is obtained. However, since the high-boiling point crosslinking agent has poor dilutability, it is first of all considered that the unsaturated polyester is required to have a relatively small molecular weight and to be easily dissolved. The prior art route for preparing low molecular weight unsaturated polyester resins is:
(1) alcohol excess method: the molecular weight of the polymer is adjusted through the excess ratio of the dihydric alcohol, and the synthesized unsaturated polyester contains more terminal hydroxyl groups and is easy to absorb water and hydrolyze; the molecular weight of the product is not even, and the content of free monomers is large; both of them affect the mechanical strength and the insulating property of the cured product of the unsaturated polyester resin.
(2) Single acid, alcohol or ester capping. The terminal hydroxyl group or terminal carboxyl group of the block polymer is generally used, for example, benzoic acid, a benzoic acid glycol ester, neopentyl alcohol, or imino alcohol. The end-capping method reduces the number of terminal hydroxyl groups and improves the water resistance, but because the linear molecular weight of the ester polymer is low, the cured product has the defects of poor crosslinking density and bonding strength, difficult drying of the surface and thin layers and the like.
CN109824874A discloses a method for producing unsaturated polyester resin, which comprises reacting benzoic acid with polyhydric alcohol under the condition of excessive alcohol to obtain hydroxy ester, and then using the hydroxy ester for end capping unsaturated polyester, thereby solving the problem of sublimation loss of benzoic acid, simplifying the production process, and improving the strength of unsaturated polyester. CN106916289A discloses a low-viscosity unsaturated resin and a preparation method thereof, which adopts raw materials comprising dibasic acid and dibasic acid anhydride, dihydric alcohol, polyhydric alcohol, monohydric alcohol and maleic anhydride, a stabilizer, an initiator and a cross-linking agent, wherein the monohydric alcohol is used as an end capping agent. Unsaturated polyester synthesized at 170-210 ℃, unsaturated polyester resin dissolved by cross-linking agents such as butanediol diacrylate, neopentyl glycol diacrylate and the like has the characteristics of low viscosity, no styrene or vinyl toluene active diluent, no more than 2% of volatile matter emission in the curing process and the like.
The crosslinking activity of the environment-friendly unsaturated polyester resin crosslinking agent is far lower than that of crosslinking agents such as styrene and the like, and the problem of surface oxygen inhibition inherent in unsaturated polyester is more serious on environment-friendly unsaturated polyester resin.
In summary, the environmental-friendly unsaturated polyester resin compounded based on low molecular weight unsaturated polyester has performance deficiencies, which cannot satisfy the following requirements: the impregnated insulating resin used by high-end equipment such as rail transit traction power, large offshore wind power and the like meets the requirements of unsaturated polyester resin, and the environment-friendly unsaturated polyester resin needs to have excellent crosslinking property and solubility and has better heat resistance, weather resistance, corrosion resistance and bonding strength after being cured.
Disclosure of Invention
The invention aims to provide an ester polymer which contains an alicyclic structure, has the characteristics of low molecular weight, easy dissolution and easy crosslinking, and is suitable for preparing low-viscosity environment-friendly resin-based composites.
Another object of the present invention is to provide an ester polymer containing an alicyclic structure, which improves the heat resistance of the resin.
It is still another object of the present invention to provide an ester polymer containing an alicyclic structure, which improves the adhesive strength of the resin.
It is still another object of the present invention to provide an ester polymer containing an alicyclic structure, which improves corrosion resistance of the resin.
The fifth object of the present invention is to provide an ester polymer containing an alicyclic structure, which improves toughness of the resin.
It is a sixth object of the present invention to provide an ester polymer containing an alicyclic structure, which improves the impact strength of the resin.
A seventh object of the present invention is to provide a method for preparing an ester polymer.
An eighth object of the present invention is to provide a resin-based composite of ester polymer, which has low viscosity, excellent weatherability, toughness, strength and heat resistance, and good compatibility with epoxy resin and other materials. The special VPI (vacuum Pressure impregnation) resin for preparation has the remarkable characteristics of high bonding strength, low dielectric loss, excellent heat resistance and the like, and is suitable for the requirements of main insulation of high-end equipment such as rail transit traction power, large offshore wind power and the like.
An ester polymer comprising, in parts by weight:
Figure BDA0002497084470000021
alicyclic polyols such as: 1, 4-cyclohexanedimethanol, spiropentanediol and hydrogenated bisphenol A, 1, 3-cyclopentanediol, 3-methyl-1, 2-cyclopentanediol, and the like, alone or in combination.
Aliphatic polyols such as: but are not limited to, neopentyl glycol, 1, 3-butanediol, 1, 4-butanediol, methylpropanediol, propylene glycol, trimethylolethane, etc., and these polyols may be used alone or in combination in the present invention.
Unsaturated acids (anhydrides) such as: but are not limited to, fumaric acid, maleic anhydride, and the like, which are used alone or in combination in the present invention.
Alicyclic polyacids (anhydrides) such as: but are not limited to, cyclohexanedicarboxylic acid, Hydrogenated Terpene Maleic Anhydride (HTMA), hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like, alone or in combination, of these alicyclic polyacids (anhydrides) are useful in the present invention.
The pyrrole compound is a pyrrole compound containing a single active hydroxyl group, such as: 1- (2-hydroxyethyl) pyrrole, 1- (3-hydroxypropyl) pyrrole, and the like, which are used as an end-capping agent for adjusting molecular weight, alone or in combination, are used in the present invention.
When the ester polymer is prepared, 0.1-2 parts by weight of solid acid catalyst and 0.01-0.3 part by weight of polymerization inhibitor are added.
Solid acid catalysts such as: but are not limited to, nano zinc oxide, nano magnesium oxide, ferric chloride hexahydrate, phosphotungstic acid, tungstosilicic acid, aluminum phosphate, boron phosphate, kaolin, bentonite, montmorillonite and 5O4 2-/ZrO2And the like, which are applied to the present invention alone or in combination.
Polymerization inhibitors such as: but are not limited to hydroquinone, t-butyl catechol, benzoquinone, p-hydroxyanisole, etc., and these polymerization inhibitors may be used in the present invention alone or in combination.
A composite comprising, in parts by weight:
60-80 parts of ester polymer
20-35 parts of cross-linking agent
A cross-linking agent selected from the group consisting of methacrylic polyol esters, acrylic polyol esters, polyallyl ethers or esters, such as: but are not limited to, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, nonanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, diallyl phthalate, diallyl 1, 4-cyclohexanedicarboxylate, 4' - (1-methylethylidene) bis [2- (2-propenyl) ] phenol, hydrogenated bisphenol A diallyl ether, tetraallyloxyethane, phenylvinylsilane, and the like. Preferred crosslinking agents having high boiling point, high copolymerization activity, good curing strength and weather resistance and low viscosity include ethylene glycol dimethacrylate, cyclohexanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, tetraallyloxyethane, hydrogenated bisphenol A diallyl ether, and 1, 4-diallyl cyclohexanedicarboxylate. These crosslinking agents may be used in the present invention alone or in combination.
The ester polymer of the present invention is prepared as follows:
according to parts by weight, firstly adding alicyclic polyhydric alcohol, aliphatic polyhydric alcohol, unsaturated acid or unsaturated anhydride, alicyclic polybasic acid or alicyclic polybasic anhydride and a solid acid catalyst into a polymerization reaction kettle, heating to 150-180 ℃ for esterification reaction for 3-5 hours until the acid value of a reactant is 100-250 mgKOH/g, then adding a pyrrole compound, reacting for 1-3 hours at 160-180 ℃, heating to 195-200 ℃, keeping the temperature until the acid value is less than 35mgKOH/g, preferably selecting the end-point acid value to be 27-35 mgKOH/g, controlling the temperature to be 180-220 ℃, gradually increasing the vacuum degree of the reaction kettle to be not less than 800Pa, preferably not less than 500Pa at 195-200 ℃, keeping vacuum distillation for 30-60 minutes, and selecting the acid value of the end-point reactant to be not more than 20mgKOH/g, preferably not more than 15 mgKOH/g.
The preparation method of the liquid compound of the ester polymer of the present invention is as follows:
cooling the ester polymer to 80-170 ℃, particularly 130-150 ℃, adding a polymerization inhibitor, mixing for 3-30 minutes, particularly 5-10 minutes, discharging into a dilution kettle added with a cross-linking agent, mixing for 20-120 minutes at 20-80 ℃, particularly 30-50 ℃, filtering with a 5-10 micron filter screen, and discharging.
The ester polymer can be used for a motor and used as main insulation, and the electrical property and the curing strength of the product are effectively improved.
Compared with the prior art, the invention has at least the following advantages:
the invention adopts monofunctional pyrrole compound to balance functionality to control molecular weight and molecular structure of ester polymer, and has the following remarkable effects:
(1) hydroxyl of the pyrrole compound with monohydroxy function has good esterification reaction activity, so that the molecular structure of the ester polymer is uniform, the number of terminal hydroxyl of the ester polymer is effectively reduced, and the water resistance and the corrosion resistance are improved;
(2) the divinyl in the pyrrole compound molecule can participate in free radical polymerization or ionic polymerization during curing to be crosslinked with double bonds or epoxy groups, so that the phenomenon of 'surface oxygen inhibition' of unsaturated polyester can be obviously improved, the crosslinking density and the crosslinking completeness are improved, and the strength of a cured product is improved.
(3) The ester polymer modified by the pyrrole compound has better toughness and cohesiveness to other materials.
The ester polymer of the present invention has alicyclic unsaturated polyester resin with excellent weather resistance, corrosion resistance, heat resistance and mechanical strength, and excellent compatibility with crosslinking agent and epoxy resin.
The solid acid catalyst adopted by the invention effectively accelerates the esterification reaction speed, improves the conversion rate, ensures that the molecular weight of the ester polymer is uniform, reduces the residual micromolecules, and ensures the curing degree, the mechanical strength, the medium corrosion resistance and the insulating property of the final cured product.
The cross-linking agent adopted in the invention has high boiling point, high copolymerization activity and low viscosity, thereby not only reducing the viscosity of the compound liquid resin, but also improving the strength and toughness of a cured product.
The compound liquid resin formed by the ester polymer and the cross-linking agent or the environment-friendly VPI resin-based active compound prepared by compounding the compound liquid resin used for modifying epoxy resin has excellent compatibility and cooperative curing property, and cured products have the characteristics of high bonding strength, low high-temperature dielectric loss, good heat resistance, weather resistance and corrosion resistance and the like, and are suitable for main insulation, such as: rail transit traction power equipment and large-scale offshore wind power and other high-end equipment.
Detailed Description
The technical solution of the present invention is described in detail below. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
220g of 1, 4-cyclohexanedimethanol, 50g of hydrogenated bisphenol A, 15g of neopentyl glycol, 16g of 1, 3-butanediol, 100g of fumaric anhydride, 115g of cyclohexanedicarboxylic acid, 23g of hydrogenated terpene maleic anhydride and 10g of SO4 2-/ZrO2The type solid acid catalyst is put into a three-neck flask, heated to 160 ℃, kept warm for 1 hour, heated to 170 ℃, kept warm for 1 hour, heated to 180 ℃, kept warm for 1.5 hours, then 20g of 1- (2-hydroxyethyl) pyrrole is added, reacted for 1 hour at 160-180 ℃, heated to 195-200 ℃, kept warm for 2 hours, then the acid value is 32mgKOH/g, kept warm for 195-200 ℃, the vacuum degree is smoothly increased to 450Pa within 20 minutes, and the acid value of the reactant is kept 13mgKOH/g after vacuum distillation for 30 minutes.
The above ester polymer was cooled to 130 ℃ and 1g of hydroquinone as a polymerization inhibitor was added thereto, and after mixing for 5 minutes, it was charged into a coolable dilution vessel to which 300g of a crosslinking agent (100 g of ethylene glycol dimethacrylate, 70g of 1, 6-hexanediol dimethacrylate, 100g of 1, 4-diallyl cyclohexanedicarboxylate and 30g of tetraallyloxyethane) had been added, and mixed at 50 ℃ for 60 minutes. The discharge was filtered through a 5-10 micron sieve to give a liquid compound of ester polymer A1.
50g of the liquid composite A of the ester polymer prepared in the embodiment, 40g of acrylic acid modified novolac epoxy, 1g of dicumyl peroxide, 8g of zinc isooctanoate, 0.5g of cobalt naphthenate and 40g of trimethylolpropane triacrylate are pumped to 100Pa, and a corrosion-resistant and high-temperature-resistant resin-based active composite B is prepared.
When the resin is used, the resin is firstly pre-cured for 2-3 hours at 120-130 ℃, and then cured for 7-8 hours at 150-170 ℃ to form a film.
Example 2
220g of 1, 4-cyclohexanedimethanol, 50g of hydrogenated bisphenol A, 15g of neopentyl glycol, 16g of 1, 3-butanediol, 100g of fumaric anhydride, 115g of cyclohexanedicarboxylic acid, 23g of hydrogenated terpene maleic anhydride and 10g of SO4 2-/ZrO2The type solid acid catalyst is put into a three-neck flask, heated to 160 ℃ and preserved for 1 hour, heated to 170 ℃ and preserved for 1 hour, heated to 180 ℃ and preserved for 1.5 hours, then the acid value of the reactant is measured to be 155mgKOH/g, then 20g of 1- (2-hydroxyethyl) pyrrole is added, the reaction is carried out for 1 hour at 160-180 ℃, heated to 195-plus-200 ℃, the acid value is 32mgKOH/g after the heat preservation for 2 hours, the heat preservation is carried out for 195-plus-200 ℃, the vacuum degree is smoothly increased to 450Pa within 20 minutes, and the acid value of the reactant is kept to be 13mgKOH/g after the vacuum distillation is carried out for 30 minutes.
The above ester polymer was cooled to 130 ℃ and 1g of hydroquinone as a polymerization inhibitor was added thereto, and after mixing for 5 minutes, it was charged into a coolable dilution vessel to which 300g of a crosslinking agent (100 g of ethylene glycol dimethacrylate, 100g of 1, 6-hexanediol dimethacrylate and 100g of 1, 4-diallyl cyclohexanedicarboxylate) had been added, and mixed at 50 ℃ for 60 minutes. The discharge was filtered through a 5-10 micron sieve to give a liquid compound of ester polymer A2.
Example 3
Putting 220g of 1, 4-cyclohexanedimethanol, 50g of hydrogenated bisphenol A, 15g of neopentyl glycol, 16g of 1, 3-butanediol, 100g of fumaric anhydride, 115g of cyclohexanedicarboxylic acid and 23g of hydrogenated terpene maleic anhydride into a three-neck flask, heating to 160 ℃, keeping the temperature for 1 hour, heating to 170 ℃, keeping the temperature for 1 hour, heating to 180 ℃, keeping the temperature for 1.5 hours, measuring the acid value of the reactant to be 155mgKOH/g, then adding 20g of 1- (2-hydroxyethyl) pyrrole, reacting at 160-180 ℃ for 1 hour, heating to 195-200 ℃, keeping the acid value to be 32mgKOH/g after 2 hours, keeping the temperature to be 195-200 ℃, smoothly increasing the vacuum degree to 450Pa within 20 minutes, and keeping the acid value of the reactant to be 13mgKOH/g after vacuum distillation for 30 minutes.
The above ester polymer was cooled to 130 ℃ and 1g of hydroquinone as a polymerization inhibitor was added thereto, and after mixing for 5 minutes, it was charged into a coolable dilution vessel to which 300g of a crosslinking agent (100 g of ethylene glycol dimethacrylate, 70g of 1, 6-hexanediol dimethacrylate, 100g of 1, 4-diallyl cyclohexanedicarboxylate and 30g of tetraallyloxyethane) had been added, and mixed at 50 ℃ for 60 minutes. The discharge was filtered through a 5-10 micron sieve to give a liquid compound of ester polymer A3.
Example 4
220g of 1, 4-cyclohexanedimethanol, 50g of hydrogenated bisphenol A, 15g of neopentyl glycol, 16g of 1, 3-butanediol, 100g of fumaric anhydride, 115g of cyclohexanedicarboxylic acid, 23g of hydrogenated terpene maleic anhydride and 10g of SO4 2-/ZrO2The type solid acid catalyst is put into a three-neck flask, heated to 160 ℃, kept warm for 1 hour, heated to 170 ℃, kept warm for 1 hour, heated to 180 ℃, kept warm for 1.5 hours, then the acid value of the reactant is measured to be 155mgKOH/g, the reaction is continued for 1 hour at 160-180 ℃, heated to 195 minus one year 200 ℃, kept warm for 2 hours, the acid value is 32mgKOH/g, kept warm for 195 minus one year 200 ℃, the vacuum degree is stably increased to 450Pa within 20 minutes, and the acid value of the reactant is kept 13mgKOH/g after vacuum distillation for 30 minutes.
The above ester polymer was cooled to 130 ℃ and 1g of hydroquinone as a polymerization inhibitor was added thereto, and after mixing for 5 minutes, it was charged into a coolable dilution vessel to which 300g of a crosslinking agent (100 g of ethylene glycol dimethacrylate, 70g of 1, 6-hexanediol dimethacrylate, 100g of 1, 4-diallyl cyclohexanedicarboxylate and 30g of tetraallyloxyethane) had been added, and mixed at 50 ℃ for 60 minutes. The discharge was filtered through a 5-10 micron sieve to give a liquid compound of ester polymer A4.
Example 5
220g of 1, 4-cyclohexanedimethanol, 50g of hydrogenated bisphenol A, 15g of neopentyl glycol, 16g of 1, 3-butanediol, 100g of fumaric anhydride, 115g of cyclohexanedicarboxylic acid, 23g of hydrogenated terpene maleic anhydride and 10g of SO4 2-/ZrO2Adding solid acid catalyst into three-neck flask, heating to 160 deg.C, maintaining for 1 hr, heating to 170 deg.C, maintaining for 1 hr, heating to 180 deg.C, maintaining for 1.5 hr, measuring the acid value of reactant to be 155mgKOH/g, and adding20g of neopentyl alcohol is added and reacted for 1 hour at 160-180 ℃, the temperature is increased to 195-plus-200 ℃, the acid value is 32mgKOH/g after the temperature is kept for 2 hours, the vacuum degree is smoothly increased to 450Pa within 20 minutes after the temperature is kept at 195-plus-200 ℃, and the acid value of the reactant is kept to be 13mgKOH/g after the vacuum distillation is carried out for 30 minutes.
The above ester polymer was cooled to 130 ℃ and 1g of hydroquinone as a polymerization inhibitor was added thereto, and after mixing for 5 minutes, it was charged into a coolable dilution vessel to which 300g of a crosslinking agent (100 g of ethylene glycol dimethacrylate, 70g of 1, 6-hexanediol dimethacrylate, 100g of 1, 4-diallyl cyclohexanedicarboxylate and 30g of tetraallyloxyethane) had been added, and mixed at 50 ℃ for 60 minutes. The discharge was filtered through a 5-10 micron sieve to give a liquid compound of ester polymer A5.
Example 6
Putting 120g of diethylene glycol, 100g of neopentyl glycol, 82g of propylene glycol, 160g of fumaric anhydride, 45g of sebacic acid and 85g of succinic acid into a three-neck flask, heating to 160 ℃, keeping the temperature for 1 hour, heating to 170 ℃, keeping the temperature for 1 hour, heating to 180 ℃, reacting until the acid value of a reactant is 13mgKOH/g, smoothly increasing the vacuum degree to 450Pa within 20 minutes, and keeping the acid value of the reactant to be 13mgKOH/g after vacuum distillation is carried out for 30 minutes.
The ester polymer was cooled to 130 ℃ and 1g of hydroquinone as a polymerization inhibitor was added, and after mixing for 5 minutes, the mixture was charged into a coolable dilution vessel to which 300g of a crosslinking agent (100 g of ethylene glycol dimethacrylate, 70g of 1, 6-hexanediol dimethacrylate, 100g of 1, 4-diallyl cyclohexanedicarboxylate, and 30g of tetraallyloxyethane) had been added, and mixed at 50 ℃ for 60 minutes. The discharge was filtered through a 5-10 micron sieve to give a liquid compound of ester polymer A6.
Example 7
The results of tests conducted after completely curing the liquid composites A of the ester polymers prepared in examples 1 to 6 are shown in Table 1.
TABLE 1
Figure BDA0002497084470000061
Example 8
The resin-based active composite B of example 1 was subjected to a performance test in accordance with the national standard (GBT 15022.2-2017 part 2 of resin-based active composite for electrical insulation: test method), wherein the wet heat resistance test conditions were humidity 85% and temperature 85 ℃. In a high-temperature and low-temperature environment, the temperature is reduced to-40 ℃ for 2h at normal temperature, the temperature is kept for 6 h, the temperature is increased to 130 ℃, and the temperature is kept for 1h, which is a cycle period.
The resin-based active compound prepared in example 1 is tested for relevant properties, the viscosity is measured to be 123s, the resin-based active compound has good permeability, can be used for VPI paint dipping, has the volatile content of less than 1%, the normal-temperature bonding strength of 248N, the bonding strength at 155 ℃ in a hot state of 67.6N, the normal dielectric loss of 0.38 and the hot dielectric loss of 1.32, and has no cracking and falling of a paint film in 12 cycles of cold and hot circulation.
The unsaturated ester polymer prepared in each embodiment has the characteristics of low viscosity, resistance to damp and heat, low volatility, fast curing, high strength and the like, and can effectively improve the electrical performance and the curing strength of a product by introducing a solid acid catalyst and a monofunctional pyrrole compound as an end-capping agent.

Claims (15)

1. An ester polymer which is a low viscosity unsaturated polyester characterized by comprising, in parts by weight;
Figure FDA0002497084460000011
2. the ester polymer of claim 1, further comprising a solid acid catalyst and a polymerization inhibitor.
3. The ester polymer of claim 2, wherein the solid acid catalyst is selected from the group consisting of nano zinc oxide, nano magnesium oxide, ferric chloride hexahydrate, phosphotungstic acid, tungstosilicic acid, aluminum phosphate, boron phosphate, kaolin, bentonite, montmorillonite and SO4 2-/ZrO2One or more of them.
4. An ester polymer according to claim 2, wherein the polymerization inhibitor is selected from one or more of hydroquinone, t-butyl catechol, benzoquinone and p-hydroxyanisole.
5. An ester polymer according to claim 1, wherein said alicyclic polyol is selected from one or more of 1, 4-cyclohexanedimethanol, spiropentanediol and hydrogenated bisphenol a, 1, 3-cyclopentanediol and 3-methyl-1, 2-cyclopentanediol.
6. The ester polymer according to claim 1, wherein the aliphatic polyhydric alcohol is one or more selected from the group consisting of neopentyl glycol, 1, 3-butanediol, 1, 4-butanediol, methylpropanediol, propylene glycol, and trimethylolethane.
7. The ester polymer of claim 1 wherein the unsaturated anhydride is selected from the group consisting of fumaric acid, maleic acid, and the corresponding anhydrides.
8. The ester polymer according to claim 1, wherein said azole compound is selected from one or more of 1- (2-hydroxyethyl) azole and 1- (3-hydroxypropyl) azole.
9. An electric machine comprising the ester polymer according to any one of claims 1 to 8.
10. A compound is characterized by comprising the following components in parts by weight:
60-80 parts of ester polymer
20-35 parts of a crosslinking agent.
11. The composite of claim 10, wherein the crosslinking agent is selected from the group consisting of methacrylic polyol esters, acrylic polyol esters, polyallyl ethers and esters.
12. The composite of claim 10, wherein said crosslinking agent has a boiling point greater than 150 ℃.
13. The composite of claim 10, wherein the cross-linking agent is selected from the group consisting of ethylene glycol dimethacrylate, cyclohexanediol dimethacrylate, 1, 6 hexanediol dimethacrylate, tetraallyloxyethane, hydrogenated bisphenol a diallyl ether, and 1, 4-diallyl cyclohexanedicarboxylate.
14. The composite according to claim 10, wherein said crosslinking agent comprises 5 to 20 wt% tetraallyloxyethane.
15. Use of a complex according to claim 10 in a VPI process.
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