CN107936185A - A kind of modified unsaturated polyester resin and preparation method thereof - Google Patents

A kind of modified unsaturated polyester resin and preparation method thereof Download PDF

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Publication number
CN107936185A
CN107936185A CN201711374783.XA CN201711374783A CN107936185A CN 107936185 A CN107936185 A CN 107936185A CN 201711374783 A CN201711374783 A CN 201711374783A CN 107936185 A CN107936185 A CN 107936185A
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unsaturated polyester
acid
dimer
fatty acid
resistance
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冯光炷
郭妍婷
黄雪
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Zhongkai University of Agriculture and Engineering
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Zhongkai University of Agriculture and Engineering
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G63/78—Preparation processes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a kind of preparation method of modified unsaturated polyester resin, phthalic anhydride is substituted with dimer fatty acid moieties, toughness reinforcing filler is used as using dimer (fatty acid) yl, added with situ aggregation method, styrene is replaced to make unsaturated polyester resin crosslinking agent with acrylate moiety, carry out toughened unsaturated polyester resin, widen its application range, while also increase the application of dimer (fatty acid) yl.Meanwhile invention additionally discloses a kind of modified unsaturated polyester resin being prepared by the preparation method.

Description

A kind of modified unsaturated polyester resin and preparation method thereof
Technical field
The present invention relates to a kind of unsaturated polyester resin and preparation method thereof, especially a kind of modified unsaturated polyester resin And preparation method thereof.
Background technology
Unsaturated polyester resin (Unsaturated polyester resin, UPR) be by unsaturated polyacid (or acid Acid anhydride) with saturated polyol after polycondensation reaction, be dissolved in a kind of multi-functional thermosetting resin formed in cross-linking monomer.Because of its valency Lattice are cheap, raw material is easy to get, production technology is easy, function admirable, have been widely used in the neck such as chemical industry, building, traffic and electronics Domain.But there is highly cross-linked rigid benzene ring structure, molecule interchain sliding scale is small, causes solidfied material after curable unsaturated polyester There are the shortcomings of toughness is low, brittleness is big, inflammable and shrinking percentage is high, its application in production practices significantly limit.With The development of UPR toughening technologies, it experienced the stages such as nano-particle toughening, fiber reinforced, elastic body toughening and vegetable oil toughness reinforcing.
The hot spot of the research of Green Polymer Material always domestic and international investigation of materials, including plant oil based polymers, life Thing synthesizes macromolecule and starch-resin etc..Vegetable oil source enriches, and is the desirable feedstock for preparing coating, thermosetting resin.In recent years Come, the research in relation to plant oil modified resin is very active, and modified resin is applied well in multiple fields.But utilize two It is less that polyglycerol fatty acid carries out unsaturated polyester resin copolymerization toughening modifying.
Dimer (fatty acid) yl (Dimer fatty acid, DFA) abbreviation dimeric dibasic acid, by unrighted acid (such as oleic acid, sub- oil Acid) or unsaturated fatty acid ester reacted and generated by Diels-Alder, there are two carboxyls, multiple unsaturated double-bonds and longer Fatty segment, the pliability, solvent resistance and heat endurance of composite material can be improved.China has abundant soybean, cotton The resources such as seed, as the development of oil prodution industry and molecular distillation technique are applied to the breakthrough of DFA purification techniques, using DFA as changing Property agent or raw material be modified and develop new UPR materials, can not only utilize the aliphatic acid resource of China's abundant, but also can carry The multiple performance of high UPR materials, widens the application field of UPR materials.Meanwhile dimeric dibasic acid has environment friend as living resources Good property and biodegradability, are expected to become a kind of plasticized modifier of environment-friendly type.
Unsaturated polyester resin brittleness is big, toughness is low, limits its application range to a certain extent；Main cause is：Adjacent benzene Dicarboxylic acid anhydride contains phenyl ring so that has highly cross-linked rigid benzene ring structure after curable unsaturated polyester, molecule interchain slides model Enclose small, causing solidfied material, there are the shortcomings of toughness is low, brittleness is big.
The content of the invention
Based on this, provided a kind of modified unsaturated it is an object of the invention to overcome above-mentioned the deficiencies in the prior art part Polyester resin.
To achieve the above object, the technical solution used in the present invention is：A kind of preparation of modified unsaturated polyester resin Method, comprises the following steps：
(1) dimer (fatty acid) yl, phthalic anhydride, 1,2-PD, catalyst are separately added into reaction vessel, is first risen When reaction 0.5~1.5 is small at warm to 160~180 DEG C, 100~120 DEG C are then cooled to, after adding maleic anhydride, then is risen Temperature to vacuumize at 120~200 DEG C reaction 3~5 it is small when, obtain dimer (fatty acid) yl modified unsaturated polyester；Wherein, the step (1) in reactant, the molar ratio of acids and alcohols is：Acids：Alcohols=1：(1~1.5), the acids include dimer fatty Acid, phthalic anhydride and maleic anhydride, the alcohols are 1,2-PD；The molar ratio of saturated acid and unsaturated acids For：Saturated acid：Unsaturated acids=(2~2.5):1, the saturated acid includes dimer (fatty acid) yl and phthalic anhydride, it is described not Saturated acid is maleic anhydride；
(2) after dimer (fatty acid) yl modified unsaturated polyester cooling obtained by step (1), resistance is sequentially added into reaction vessel Poly- agent, crosslinking agent, accelerating agent, initiator, stir evenly, when then curing 2-8 is small at 60-160 DEG C, up to of the present invention Modified unsaturated polyester resin.
Preferably, in the reactant in the step (1), the molar ratio of acids and alcohols is：Acids：Alcohols=1：1.3； The molar ratio of saturated acid and unsaturated acids is：Saturated acid：Unsaturated acids=2.4：1.
Acid alcohol ratio is 1:When 1.3, the esterification yield of polyester is maximum, i.e., the extent of reaction is maximum.Saturated acid (is handed over unsaturated acids Join density) ratio be 2.4:When 1, resin property is optimal.
Preferably, the crosslinking agent in the step (2) is at least one of styrene, acrylic acid.
It is highly preferred that the molar ratio of step (2) styrene and acrylic acid is：Styrene：Acrylic acid=(10-0): (0-10)。
It is highly preferred that the molar ratio of step (2) styrene and acrylic acid is：Styrene：Acrylic acid=5:5.
Styrene toxicity is big, so it is 5 to select acrylate moiety to substitute styrene as crosslinking agent, both final molar ratios:5 When, resin property is optimal.
Preferably, the molar ratio of the crosslinking agent and the maleic anhydride in the step (1) in the step (2) is： Crosslinking agent：Maleic anhydride=(1.5-5)：1.
It is highly preferred that the molar ratio of the crosslinking agent and the maleic anhydride in the step (1) in the step (2) For：Crosslinking agent：Maleic anhydride=3.5：1.
Preferably, in the step (1), Mole percent of the dimer (fatty acid) yl in the step (1) reactant contains Measure as 3~11%.
It is highly preferred that in the step (1), Mole percent of the dimer (fatty acid) yl in the step (1) reactant Content is 6%.
Preferably, in the step (1), the catalyst is at least one in p-methyl benzenesulfonic acid, stannous chloride, the concentrated sulfuric acid Kind, mass percentage of the catalyst in step (1) described reactant is 1~2.2%；It is described in the step (2) Polymerization inhibitor is hydroquinone, and the accelerating agent is cobalt naphthenate, and the initiator is methyl ethyl ketone peroxide, the matter of the polymerization inhibitor 0.05% of the dimer (fatty acid) yl modified unsaturated polyester quality obtained by step (1) is measured, the quality of the accelerating agent is step (1) The 1% of gained dimer (fatty acid) yl modified unsaturated polyester quality, the quality of the initiator is step (1) gained dimer (fatty acid) yl The 2% of modified unsaturated polyester quality.
Meanwhile the present invention also provides the modified unsaturated polyester resin that a kind of preparation method is prepared.
Relative to the prior art, beneficial effects of the present invention are：
The present invention provides one kind to improve the flexible method of unsaturated polyester resin, is substituted with dimer fatty acid moieties adjacent Phthalate anhydride, using dimer (fatty acid) yl as toughness reinforcing filler, is added with situ aggregation method, replaces styrene to make with acrylate moiety Unsaturated polyester resin crosslinking agent, carrys out toughened unsaturated polyester resin, widens its application range, while also increase dimer fatty The application of acid.
The unsaturated polyester resin of the present invention being prepared has following excellent properties：Tensile strength is 11.0921MPa, elongation at break 71.05%, elasticity modulus 126.7487MPa, bending strength 12.0277MPa, Shao Family name (A) hardness is 73.0, and initial pyrolyzation temperature is 195 DEG C, water absorption rate 2.16%, and water resistance loss late is 0.44%, resistance to Acid absorptivity is 2.04%, and acid resistance loss late is 0.27%, and alkali resistance absorptivity is 14.12%, and alkali resistance loss late is 3.53%, resistance to ethanol absorptivity is 6.13%, and resistance to Ethanol loss rate is 1.57%, and resistance to toluene absorptivity is 74.12%, resistance to toluene Loss late is 25.67%.
Brief description of the drawings
Fig. 1 is a kind of preparation flow figure of modified unsaturated polyester resin of the present invention.
Embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with the drawings and specific embodiments pair The present invention is described further.
Embodiment 1
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 11.0921MPa, elongation at break 71.05%, elasticity modulus 126.7487MPa, bending strength 12.0277MPa, Shao Family name (A) hardness is 73.0, and initial pyrolyzation temperature is 195 DEG C, water absorption rate 2.16%, and water resistance loss late is 0.44%, resistance to Acid absorptivity is 2.04%, and acid resistance loss late is 0.27%, and alkali resistance absorptivity is 14.12%, and alkali resistance loss late is 3.53%, resistance to ethanol absorptivity is 6.13%, and resistance to Ethanol loss rate is 1.57%, and resistance to toluene absorptivity is 74.12%, resistance to toluene Loss late is 25.67%.
Embodiment 2
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 5% Reactant total moles quality), the molar ratio of saturated acid and unsaturated acids is 2.5:1, acid alcohol molar ratio is 1:1.5) two polyesters Fat acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen And be to slowly warm up to start to stir when reactant is in molten condition, 0.5h is reacted at 180 DEG C, stops inflated with nitrogen, is cooled to 130 DEG C, maleic anhydride is added, reaction 3h is vacuumized at 200 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=10:0 (molar ratio), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 3.2998MPa, elongation at break 33.28%, elasticity modulus 36.4325MPa, bending strength 2.8725MPa, shore (A) hardness is 61, water absorption rate 3.54%, and water resistance loss late is 0.58%, and acid resistance absorptivity is 3.04%, acid resistance damage Mistake rate is 1.89%, and alkali resistance absorptivity is 18.66%, and alkali resistance loss late is 10.95%, and resistance to ethanol absorptivity is 11.18%, resistance to Ethanol loss rate is 7.67%, and resistance to toluene absorptivity is 57.35%, and resistance to toluene loss late is 24.63%.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 6.7749MPa, elongation at break 71.68%, elasticity modulus 64.63MPa, bending strength 7.1232MPa, Shao Family name (A) hardness is 73.5, and initial pyrolyzation temperature is 201 DEG C, water absorption rate 2.04%, and water resistance loss late is 0.11%, resistance to Acid absorptivity is 1.96%, and acid resistance loss late is 0.58%, and alkali resistance absorptivity is 7.21%, and alkali resistance loss late is 4.41%, resistance to ethanol absorptivity is 5.68%, and resistance to Ethanol loss rate is 2.05%, and resistance to toluene absorptivity is 71.30%, resistance to toluene Loss late is 21.56%.
Embodiment 3
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 7% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2:1, acid alcohol molar ratio is 1:1) dimer (fatty acid) yl, neighbour Phthalate anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen and slow It is warming up to when reactant is in molten condition and starts to stir, 1.5h is reacted at 160 DEG C, stop inflated with nitrogen, be cooled to 110 DEG C, adds Maleic anhydride, reaction 5h is vacuumized at 120 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=0:10 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 7.9024MPa, elongation at break 46.90%, elasticity modulus 88.1953MPa, bending strength 8.9166MPa, shore (A) hardness is 71, water absorption rate 2.65%, and water resistance loss late is 0.36%, and acid resistance absorptivity is 2.40%, acid resistance damage Mistake rate is 0.57%, and alkali resistance absorptivity is 17.26%, and alkali resistance loss late is 4.41%, and resistance to ethanol absorptivity is 5.84%, Resistance to Ethanol loss rate is 2.45%, and resistance to toluene absorptivity is 60.93%, and resistance to toluene loss late is 22.15%.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 3.7297MPa, elongation at break 71.68%, elasticity modulus 31.6323MPa, bending strength 2.9122MPa, Shore (A) hardness is 56, and initial pyrolyzation temperature is 173 DEG C, water absorption rate 16.81%, and water resistance loss late is 6.48%, resistance to Acid absorptivity is 6.95%, and acid resistance loss late is 4.66%, and alkali resistance absorptivity is 30.41%, and alkali resistance loss late is 15.14%, resistance to ethanol absorptivity is 31.22%, and resistance to Ethanol loss rate is 7.42%, and resistance to toluene absorptivity is 95.13%, resistance to first Benzene loss late is 40.43%.
Embodiment 4
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 60 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 8.0154MPa, elongation at break 70.28%, elasticity modulus 88.4426MPa, bending strength 7.4125MPa, Shore (A) hardness is 68, and initial pyrolyzation temperature is 199 DEG C, water absorption rate 4.16%, and water resistance loss late is 0.58%, resistance to Acid absorptivity is 5.13%, and acid resistance loss late is 1.89%, and alkali resistance absorptivity is 10.49%, and alkali resistance loss late is 10.26%, resistance to ethanol absorptivity is 10.13%, and resistance to Ethanol loss rate is 6.74%, and resistance to toluene absorptivity is 68.95%, resistance to first Benzene loss late is 28.13%.
Embodiment 5
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio 2.4 of saturated acid and unsaturated acids:1, acid alcohol molar ratio is 1:Dimer (fatty acid) yl 1.3), Phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen and delay Slow be warming up to when reactant is in molten condition starts to stir, and 1h is reacted at 170 DEG C, stops inflated with nitrogen, is cooled to 120 DEG C, adds Maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 2h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 8.189MPa, elongation at break 45.69%, elasticity modulus 85.5893MPa, bending strength 8.8661MPa, Shore (A) hardness is 67, and initial pyrolyzation temperature is 183 DEG C, water absorption rate 8.83%, and water resistance loss late is 2.03%, resistance to Acid absorptivity is 3.00%, and acid resistance loss late is 1.09%, and alkali resistance absorptivity is 18.80%, and alkali resistance loss late is 10.13%, resistance to ethanol absorptivity is 17.12%, and resistance to Ethanol loss rate is 4.71%, and resistance to toluene absorptivity is 76.67%, resistance to first Benzene loss late is 57.02%.
Embodiment 6
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 8h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 5.3904MPa, elongation at break 70.83%, elasticity modulus 65.2479MPa, bending strength 5.0447MPa, Shore (A) hardness is 62.5, and initial pyrolyzation temperature is 188 DEG C, water absorption rate 13.28%, and water resistance loss late is 2.35%, Acid resistance absorptivity is 3.99%, and acid resistance loss late is 1.81%, and alkali resistance absorptivity is 18.13%, alkali resistance loss late For 13.25%, resistance to ethanol absorptivity is 21.74%, and resistance to Ethanol loss rate is 10.91%, and resistance to toluene absorptivity is 87.78%, Resistance to toluene loss late is 73.13%.
Embodiment 7
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant total moles quality), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) two polyesters Fat acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen And be to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, is cooled to 120 DEG C, Maleic anhydride is added, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=4:6 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 8.8472MPa, elongation at break 65.45%, elasticity modulus 87.0921MPa, bending strength 9.1466MPa, shore (A) hardness is 68.0, and initial pyrolyzation temperature is 192 DEG C, water absorption rate 2.61%, and water resistance loss late is 0.89%, acidproof Property absorptivity be 4.51%, acid resistance loss late is 1.11%, and alkali resistance absorptivity is 14.51%, and alkali resistance loss late is 7.17%, resistance to ethanol absorptivity is 11.77%, and resistance to Ethanol loss rate is 1.45%, and resistance to toluene absorptivity is 81.13%, resistance to first Benzene loss late is 24.16%.
Embodiment 8
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant total moles quality), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) two polyesters Fat acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen And be to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, is cooled to 120 DEG C, Maleic anhydride is added, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=6:4 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 6.5453MPa, elongation at break 82.01%, elasticity modulus 65.6363MPa, bending strength 7.9654MPa, shore (A) hardness is 70.0, and initial pyrolyzation temperature is 189 DEG C, water absorption rate 2.27%, and water resistance loss late is 0.28%, acidproof Property absorptivity be 1.99%, acid resistance loss late is 0.11%, and alkali resistance absorptivity is 8.04%, and alkali resistance loss late is 2.71%, resistance to ethanol absorptivity is 2.14%, and resistance to Ethanol loss rate is 1.62%, and resistance to toluene absorptivity is 71.76%, resistance to toluene Loss late is 26.01%.
Embodiment 9
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 3h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 10.1090MPa, elongation at break 66.50%, elasticity modulus 110.6380MPa, bending strength 11.4022MPa, Shao Family name (A) hardness is 69.0, and initial pyrolyzation temperature is 192 DEG C, water absorption rate 3.77%, and water resistance loss late is 1.07%, resistance to Acid absorptivity is 2.03%, and acid resistance loss late is 0.77%, and alkali resistance absorptivity is 15.49%, and alkali resistance loss late is 7.13%, resistance to ethanol absorptivity is 8.48%, and resistance to Ethanol loss rate is 3.66%, and resistance to toluene absorptivity is 69.95%, resistance to toluene Loss late is 36.89%.
Embodiment 10
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 5h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 8.3547MPa, elongation at break 72.53%, elasticity modulus 88.2649MPa, bending strength 8.9937MPa, shore (A) hardness is 66.0, and initial pyrolyzation temperature is 194 DEG C, water absorption rate 4.75%, and water resistance loss late is 1.02%, acidproof Property absorptivity be 2.17%, acid resistance loss late is 0.83%, and alkali resistance absorptivity is 10.49%, and alkali resistance loss late is 8.17%, resistance to ethanol absorptivity is 10.13%, and resistance to Ethanol loss rate is 2.89%, and resistance to toluene absorptivity is 78.78%, resistance to first Benzene loss late is 36.29%.
Embodiment 11
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 3% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1% (accounting for step (1) reactant gross mass) are filled with nitrogen and delay to stannous chloride Slow be warming up to when reactant is in molten condition starts to stir, and 1.5h is reacted at 160 DEG C, stops inflated with nitrogen, is cooled to 120 DEG C, adds Enter maleic anhydride, reaction 5h is vacuumized at 120 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 160 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 1.7940MPa, elongation at break 56.03%, elasticity modulus 16.4558MPa, bending strength 1.3924MPa, Shore (A) hardness is 37, water absorption rate 4.23%, and water resistance loss late is 1.01%, and acid resistance absorptivity is 13.84%, resistance to Acidity loss rate is 6.53%, and alkali resistance absorptivity is 25.68%, and alkali resistance loss late is 30.16%, and resistance to ethanol absorptivity is 26.22%, resistance to Ethanol loss rate is 16.30%, and resistance to toluene absorptivity is 87.78%, and resistance to toluene loss late is 46.69%.
Embodiment 12
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 120 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 5.4625MPa, elongation at break 62.37%, elasticity modulus 60.9793MPa, bending strength 5.9008MPa, Shore (A) hardness is 63, water absorption rate 3.82%, and water resistance loss late is 0.67%, and acid resistance absorptivity is 7.39%, acidproof Property loss late be 4.81%, alkali resistance absorptivity is 18.13%, and alkali resistance loss late is 18.41%, and resistance to ethanol absorptivity is 19.00%, resistance to Ethanol loss rate is 8.35%, and resistance to toluene absorptivity is 82.37%, and resistance to toluene loss late is 35.40%.
Embodiment 13
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio 2.4 of saturated acid and unsaturated acids:1, acid alcohol molar ratio is 1:Dimer (fatty acid) yl 1.3), Phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen and delay Slow be warming up to when reactant is in molten condition starts to stir, and 1h is reacted at 170 DEG C, stops inflated with nitrogen, is cooled to 120 DEG C, adds Maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 2h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 8.5893MPa, elongation at break 45.69%, elasticity modulus 85.5893MPa, bending strength 8.8661MPa, Shore (A) hardness is 67, water absorption rate 8.83%, and water resistance loss late is 2.03%, and acid resistance absorptivity is 3.00%, acidproof Property loss late be 1.09%, alkali resistance absorptivity is 18.80%, and alkali resistance loss late is 10.13%, and resistance to ethanol absorptivity is 17.12%, resistance to Ethanol loss rate is 4.72%, and resistance to toluene absorptivity is 76.67%, and resistance to toluene loss late is 57.02%.
Embodiment 14
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 8h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：The stretching of resin Intensity is 5.3904MPa, elongation at break 70.83%, elasticity modulus 65.2479MPa, bending strength 5.0447MPa, Shore (A) hardness is 62.5, water absorption rate 13.28%, and water resistance loss late is 2.35%, and acid resistance absorptivity is 4.00%, Acid resistance loss late is 1.81%, and alkali resistance absorptivity is 18.13%, and alkali resistance loss late is 13.25%, resistance to ethanol absorptivity For 21.74%, resistance to Ethanol loss rate is 10.91%, and resistance to toluene absorptivity is 87.78%, and resistance to toluene loss late is 60.13%.
Embodiment 15
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 3h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 10.1090MPa, elongation at break 66.50%, elasticity modulus 110.6380MPa, bending strength 11.4022MPa, Shao Family name (A) hardness is 69.0, water absorption rate 3.77%, and water resistance loss late is 1.07%, and acid resistance absorptivity is 2.03%, acidproof Property loss late be 0.77%, alkali resistance absorptivity is 15.49%, and alkali resistance loss late is 7.13%, and resistance to ethanol absorptivity is 8.48%, resistance to Ethanol loss rate is 3.66%, and resistance to toluene absorptivity is 69.95%, and resistance to toluene loss late is 36.89%.
Embodiment 16
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 5h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 8.3547MPa, elongation at break 72.53%, elasticity modulus 88.2649MPa, bending strength 8.9937MPa, shore (A) hardness is 66.0, water absorption rate 4.75%, and water resistance loss late is 1.02%, and acid resistance absorptivity is 2.17%, acid resistance Loss late is 0.83%, and alkali resistance absorptivity is 10.49%, and alkali resistance loss late is 8.17%, and resistance to ethanol absorptivity is 10.13%, resistance to Ethanol loss rate is 2.89%, and resistance to toluene absorptivity is 78.78%, and resistance to toluene loss late is 36.29%.
Embodiment 17
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 11% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 2.2% (accounting for step (1) reactant gross mass) concentrated sulfuric acid, are filled with nitrogen and slow It is warming up to when reactant is in molten condition and starts to stir, 0.5h is reacted at 180 DEG C, stop inflated with nitrogen, be cooled to 100 DEG C, adds Maleic anhydride, reaction 3h is vacuumized at 200 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=1.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 2.3847MPa, elongation at break 35.67%, elasticity modulus 22.7209MPa, bending strength 2.7070MPa, shore (A) hardness is 63.0, water absorption rate 4.50%, and water resistance loss late is 0.87%, and acid resistance absorptivity is 4.27%, acid resistance Loss late is 6.44%, and alkali resistance absorptivity is 18.12%, and alkali resistance loss late is 7.10%, and resistance to ethanol absorptivity is 8.39%, resistance to Ethanol loss rate is 8.34%, and resistance to toluene absorptivity is 75.72%, and resistance to toluene loss late is 31.38%.
Embodiment 18
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=5.0:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 3.8830MPa, elongation at break 36.40%, elasticity modulus 33.6459MPa, bending strength 3.6526MPa, shore (A) hardness is 60, water absorption rate 5.63%, and water resistance loss late is 1.03%, and acid resistance absorptivity is 4.47%, acid resistance damage Mistake rate is 5.19%, and alkali resistance absorptivity is 19.20%, and alkali resistance loss late is 9.08%, and resistance to ethanol absorptivity is 10.16%, resistance to Ethanol loss rate is 3.19%, and resistance to toluene absorptivity is 78.53%, and resistance to toluene loss late is 30.59%.
Embodiment 19
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.0:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 5.4287MPa, elongation at break 53.15%, elasticity modulus 64.4694MPa, bending strength 7.1109MPa, shore (A) hardness is 68.0, water absorption rate 3.57%, and water resistance loss late is 0.70%, and acid resistance absorptivity is 3.19%, acid resistance Loss late is 1.37%, and alkali resistance absorptivity is 16.00%, and alkali resistance loss late is 5.36%, and resistance to ethanol absorptivity is 7.21%, resistance to Ethanol loss rate is 6.95%, and resistance to toluene absorptivity is 71.08%, and resistance to toluene loss late is 28.27%.
Embodiment 20
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=4.0:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2% (accounts for step (1) products therefrom dimer (fatty acid) yl and is modified insatiable hunger With polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, then Isothermal curing 4h at 80 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 5.7386MPa, elongation at break 52.16%, elasticity modulus 71.2473MPa, bending strength 7.3431MPa, shore (A) hardness is 64.0, water absorption rate 4.20%, and water resistance loss late is 0.81%, and acid resistance absorptivity is 3.28%, acid resistance Loss late is 1.02%, and alkali resistance absorptivity is 15.21%, and alkali resistance loss late is 6.79%, and resistance to ethanol absorptivity is 9.12%, resistance to Ethanol loss rate is 2.47%, and resistance to toluene absorptivity is 73.40%, and resistance to toluene loss late is 29.19%.
Embodiment 21
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 0.5% (accounts for step (1) products therefrom dimer (fatty acid) yl to be modified not Saturated polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, so Isothermal curing 4h at 80 DEG C afterwards, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 3.9525MPa, elongation at break 70.57%, elasticity modulus 22.6254MPa, bending strength 4.0534MPa, shore (A) hardness is 44, water absorption rate 13.21%, and water resistance loss late is 6.41%, and acid resistance absorptivity is 11.00%, acid resistance Loss late is 7.34%, and alkali resistance absorptivity is 22.24%, and alkali resistance loss late is 12.06%, and resistance to ethanol absorptivity is 26.08%, resistance to Ethanol loss rate is 8.07%, and resistance to toluene absorptivity is 97.34%, and resistance to toluene loss late is 39.60%.
Embodiment 22
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 3.0% (accounts for step (1) products therefrom dimer (fatty acid) yl to be modified not Saturated polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, so Isothermal curing 4h at 80 DEG C afterwards, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 4.8622MPa, elongation at break 60.09%, elasticity modulus 52.5415MPa, bending strength 4.8752MPa, shore (A) hardness is 38, water absorption rate 11.42%, and water resistance loss late is 5.59%, and acid resistance absorptivity is 8.53%, acid resistance Loss late is 4.66%, and alkali resistance absorptivity is 21.49%, and alkali resistance loss late is 10.05%, and resistance to ethanol absorptivity is 20.15%, resistance to Ethanol loss rate is 5.86%, and resistance to toluene absorptivity is 90.92%, and resistance to toluene loss late is 56.32%.
Embodiment 23
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 1.5% (accounts for step (1) products therefrom dimer (fatty acid) yl to be modified not Saturated polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, so Isothermal curing 4h at 80 DEG C afterwards, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 7.4961MPa, elongation at break 75.34%, elasticity modulus 69.3390MPa, bending strength 8.0745MPa, shore (A) hardness is 61.0, water absorption rate 6.15%, and water resistance loss late is 2.79%, and acid resistance absorptivity is 5.04%, acid resistance Loss late is 3.66%, and alkali resistance absorptivity is 15.58%, and alkali resistance loss late is 10.47%, and resistance to ethanol absorptivity is 10.22%, resistance to Ethanol loss rate is 4.25%, and resistance to toluene absorptivity is 80.07%, and resistance to toluene loss late is 27.08%.
Embodiment 24
A kind of embodiment of unsaturated polyester resin preparation method of the present invention, preparation method described in the present embodiment are：
(1) certain proportioning is added into 500mL four-hole boiling flasks, and (mole dosage of dimer (fatty acid) yl (accounts for step (1) for 6% Reactant integral molar quantity), the molar ratio of saturated acid and unsaturated acids is 2.4:1, acid alcohol molar ratio is 1:1.3) dimer fatty Acid, phthalic anhydride, 1,2-PD and 1.9% (accounting for step (1) reactant gross mass) p-methyl benzenesulfonic acid, are filled with nitrogen simultaneously It is to slowly warm up to start to stir when reactant is in molten condition, 1h is reacted at 170 DEG C, stops inflated with nitrogen, be cooled to 120 DEG C, add Enter maleic anhydride, reaction 4h is vacuumized at 170 DEG C, obtains dimer (fatty acid) yl modified unsaturated polyester；
(2) after polyester cooling, sequentially add hydroquinone of polymerization retarder 0.05% and (account for two polyester of step (1) products therefrom Fat acid modified unsaturated polyester quality), crosslinking styrene and acrylic acid (styrene：Acrylic acid=5:5 (molar ratios), crosslinking Agent：Maleic anhydride=3.5:1 (molar ratio)), accelerating agent cobalt naphthenate 1% (account for step (1) products therefrom dimer (fatty acid) yl Modified unsaturated polyester quality), initiator methyl ethyl ketone peroxide 2.5% (accounts for step (1) products therefrom dimer (fatty acid) yl to be modified not Saturated polyester quality), after stirring evenly, pour into scribble releasing agent atoleine from molding jig, stand 24h at room temperature, so Isothermal curing 4h at 80 DEG C afterwards, obtains dimer (fatty acid) yl modified unsaturated polyester resin after cooling.
The unsaturated polyester resin being prepared by above-mentioned preparation method, has following excellent properties：Tensile strength is 8.2283MPa, elongation at break 63.64%, elasticity modulus 65.6401MPa, bending strength 9.3158MPa, shore (A) hardness is 63.0, water absorption rate 8.83%, and water resistance loss late is 3.02%, and acid resistance absorptivity is 5.26%, acid resistance Loss late is 1.77%, and alkali resistance absorptivity is 18.98%, and alkali resistance loss late is 7.48%, and resistance to ethanol absorptivity is 12.92%, resistance to Ethanol loss rate is 3.27%, and resistance to toluene absorptivity is 75.17%, and resistance to toluene loss late is 37.08%.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should Understand, can be to technical scheme technical scheme is modified or replaced equivalently, without departing from the essence of technical solution of the present invention And scope.

Claims (10)

1. a kind of preparation method of modified unsaturated polyester resin, it is characterised in that comprise the following steps：
(1) dimer (fatty acid) yl, phthalic anhydride, 1,2-PD, catalyst are separately added into reaction vessel, is first warming up to When reaction 0.5~1.5 is small at 160~180 DEG C, 100~120 DEG C are then cooled to, after adding maleic anhydride, then is warming up to Vacuumized at 120~200 DEG C reaction 3~5 it is small when, obtain dimer (fatty acid) yl modified unsaturated polyester；Wherein, the step (1) Reactant in, the molar ratio of acids and alcohols is：Acids：Alcohols=1：(1~1.5), the acids include dimer (fatty acid) yl, Phthalic anhydride and maleic anhydride, the alcohols are 1,2-PD；The molar ratio of saturated acid and unsaturated acids is：It is full And acid：Unsaturated acids=(2~2.5):1, the saturated acid includes dimer (fatty acid) yl and phthalic anhydride, the unsaturated acids For maleic anhydride；
(2) after dimer (fatty acid) yl modified unsaturated polyester cooling obtained by step (1), inhibition is sequentially added into reaction vessel Agent, crosslinking agent, accelerating agent, initiator, stir evenly, and when then curing 2-8 is small at 60-160 DEG C, change up to of the present invention Property unsaturated polyester resin.
2. the preparation method of modified unsaturated polyester resin as claimed in claim 1, it is characterised in that in the step (1) Reactant in, the molar ratio of acids and alcohols is：Acids：Alcohols=1：1.3；The molar ratio of saturated acid and unsaturated acids is： Saturated acid：Unsaturated acids=2.4：1.
3. the preparation method of modified unsaturated polyester resin as claimed in claim 1, it is characterised in that in the step (2) Crosslinking agent be styrene, at least one of acrylic acid.
4. the preparation method of modified unsaturated polyester resin as claimed in claim 1, it is characterised in that step (2) benzene The molar ratio of ethene and acrylic acid is：Styrene：Acrylic acid=(10-0):(0-10).
5. the preparation method of modified unsaturated polyester resin as claimed in claim 1, it is characterised in that in the step (2) The molar ratio of crosslinking agent and the maleic anhydride in the step (1) be：Crosslinking agent：Maleic anhydride=(1.5-5)： 1。
6. the preparation method of modified unsaturated polyester resin as claimed in claim 1, it is characterised in that in the step (2) The molar ratio of crosslinking agent and the maleic anhydride in the step (1) be：Crosslinking agent：Maleic anhydride=3.5：1.
7. the preparation method of modified unsaturated polyester resin as claimed in claim 1, it is characterised in that in the step (1), Molar content of the dimer (fatty acid) yl in the step (1) reactant is 3~11%.
8. the preparation method of modified unsaturated polyester resin as claimed in claim 7, it is characterised in that in the step (1), Molar content of the dimer (fatty acid) yl in the step (1) reactant is 6%.
9. the preparation method of modified unsaturated polyester resin as claimed in claim 1, it is characterised in that in the step (1), The catalyst is at least one of p-methyl benzenesulfonic acid, stannous chloride, the concentrated sulfuric acid, and the catalyst is described anti-in step (1) It is 1~2.2% to answer the mass percentage in thing；In the step (2), the polymerization inhibitor is hydroquinone, the accelerating agent For cobalt naphthenate, the initiator is methyl ethyl ketone peroxide, and quality dimer (fatty acid) yl obtained by step (1) of the polymerization inhibitor changes Property unsaturated polyester (UP) quality 0.05%, the quality of the accelerating agent dimer (fatty acid) yl obtained by step (1) is modified unsaturated poly- The 1% of ester quality, the quality of the initiator is the 2% of step (1) gained dimer (fatty acid) yl modified unsaturated polyester quality.
A kind of 10. modified unsaturated polyester resin being prepared by any one of claim 1~9 preparation method.
CN201711374783.XA 2017-12-15 2017-12-15 A kind of modified unsaturated polyester resin and preparation method thereof Pending CN107936185A (en)

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