CN109337054A - Soybean oil modified unsaturated polyester resin and preparation method thereof - Google Patents
Soybean oil modified unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN109337054A CN109337054A CN201811251595.2A CN201811251595A CN109337054A CN 109337054 A CN109337054 A CN 109337054A CN 201811251595 A CN201811251595 A CN 201811251595A CN 109337054 A CN109337054 A CN 109337054A
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- 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
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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Abstract
The present invention provides a kind of soybean oil modified unsaturated polyester resins and preparation method thereof, comprising the following steps: (1) soybean oil, dihydric alcohol, catalyst is added to stirring in reaction kettle and is warming up to 200-240 DEG C, and keep the temperature 2-4h, obtain intermediate；(2) by dihydric alcohol, binary acid, 1:1.1-1.5 is added in reaction kettle stirring and is warming up to 190-210 DEG C in molar ratio, reaction dehydration to system acid value to 100mgKOH/g hereinafter, reactant A；(3) intermediate described in step (1) is added in the reactant A of step (2), stirring is warming up to 190-210 DEG C, obtains resin；(4) resin described in step (3) is cooled to 130-160 DEG C, is mixed with polymerization inhibitor, styrene, control temperature between 55-70 DEG C, be cooled to 45 DEG C hereinafter, addition promotor.Soybean oil modified unsaturated polyester resin function admirable of the invention.
Description
Technical field
The invention belongs to unsaturated polyester resin field, it is related to a kind of soybean oil modified unsaturated polyester resin and its preparation
Method can be widely applied to the industries such as poly-putty base, artificial marble and craftwork.
Background technique
Unsaturated polyester resin is usually spent glycol, 1,2- propylene glycol, diglycol, maleic anhydride, neighbour
Phthalate anhydride etc. is diluted in styrene after melt polycondensation to certain molecular weight at 180-220 DEG C, because it has system
Standby simple process, the advantage that processing performance is good, cost performance is high, are widely used in artificial stone, glass reinforced plastic, craftwork, button, atom
The fields such as ash, woodwork coating.But due to the inhibition of oxygen in air, surface drying is poor when use, needs to add the tables such as paraffin
Dry auxiliary agent increases the post-processing program of manufactured goods, in addition the common longer flexible chain element of unsaturated polyester resin such as oneself two
There is larger limitation in the field that acid, dipropylene glycol etc. apply it because price is more expensive, and conventional unsaturated polyester resin is due to nothing
The introducing of flexible molecule chain, resin toughness is poor, brittle, therefore introduces a kind of flexible chain ingredient that cost performance is high for unsaturation
There is higher application value for polyester resin.
Traditional unsaturated polyester resin is produced using petrochemical material, and wherein main raw material(s) is petroleum, coal
Retrofit, but the continuous reduction of the cost and petrochemical materials constantly risen, but also as soybean oil is this can
Regenerated resources are more attractive as alternate resources.
Summary of the invention
In view of the problems of the existing technology, use soybean oil soft as Material synthesis the object of the present invention is to provide a kind of
Good toughness, unsaturated polyester resin with good surface drying performance and preparation method thereof.
The main component of soybean oil is linoleic acid, oleic acid, palmitinic acid and stearic glyceride, and carbochain has 16-18
Carbon, therefore flexibility is good and solidification after-contraction deformation is smaller；In addition soybean oil is drying oil, wherein containing unsaturation in containing
Double bond can increase the empty stemness that resin is made.
Soybean oil modified unsaturated polyester resin of the invention, is achieved through the following technical solutions:
A kind of preparation method of soybean oil modified unsaturated polyester resin, comprising the following steps:
(1) soybean oil, dihydric alcohol, catalyst are added to stirring in reaction kettle and are warming up to 200-240 DEG C, and keep the temperature 2-
4h obtains intermediate；The molar ratio of dihydric alcohol described in step (1) and soybean oil is 3.0-7.0:1, and the catalyst accounts for soybean
The 0.01-0.10% (preferably 0.01-0.05%) of oil and dihydric alcohol gross mass；
(2) by dihydric alcohol, binary acid (including binary acid and/or dibasic acid anhydride), 1:1.1-1.5 is added to instead in molar ratio
Answer in kettle stirring to be warming up to 190-210 DEG C, reaction dehydration to system acid value to 100mgKOH/g hereinafter, reactant A, wherein institute
Binary acid is stated including at least maleic anhydride；
(3) intermediate described in step (1) being added in the reactant A of step (2), stirring is warming up to 190-210 DEG C,
Isothermal reaction is dehydrated to acid value 15-40mgKOH/g (such as 20-35mgKOH/g), obtains resin；
(4) resin described in step (3) is cooled to 130-160 DEG C, is mixed with polymerization inhibitor, styrene (for example, can be first
Styrene is added in dilution kettle, and polymerization inhibitor is added and is uniformly dispersed, then by the slow thinning of resin after cooling to diluting kettle
In mixed), control temperature between 55-70 DEG C, be cooled to 45 DEG C hereinafter, addition promotor, wherein the styrene and
The mass ratio of resin is 0.2-0.8:1, and the amount of polymerization inhibitor is 50-350ppm (such as the 50- of styrene and resin gross mass
100ppm, 100-150ppm, 150-200ppm, 200-250ppm, 250-300ppm, 300-350ppm)；The amount of promotor is resistance
Poly- agent, styrene and resin gross mass 0.2-2%.
Further, the dihydric alcohol is ethylene glycol, 1,2-PD, diglycol, 2- methyl-1,3- the third two
At least one of alcohol, 1,4- butanediol, 2,2- dimethyl -1,3- propylene glycol.
It is further preferred that the molar ratio of dihydric alcohol described in step (1) and soybean oil is 3.9-6.0:1, more preferably
4.2-5.4:1.
It is further preferred that the molar ratio of dihydric alcohol described in step (2) and binary acid is 1:1.15-1.35.
It is further preferred that the mass ratio of styrene described in step (4) and resin is 0.4-0.6:1.
Further, the dosage of promotor accounts for the 0.2-1.2% of polymerization inhibitor, styrene and resin gross mass in step (4),
It is further 0.2-1.0%.
Further, the catalyst be dibutyl tin dilaurate, certain herbaceous plants with big flowers acid lithium, lithium titanate, in n-BuLi at least
It is a kind of.
Optionally, binary acid is monounsaturated dicarboxylic acid and/or unsaturated dibasic acid.
It is alternatively possible to substitute maleic anhydride with maleic acid (fumaric acid).The binary acid includes maleic
Dicarboxylic anhydride, maleic acid.
Further, the binary acid further include phthalic anhydride, tetrabydrophthalic anhydride, terephthalic acid (TPA),
At least one of phthalic acid, hexahydrophthalic anhydride.
Further, molar ratio shared by maleic anhydride described in step (2) is 0.6-1.5, such as dihydric alcohol, two
1:1.1-1.5 is mixed first acid in molar ratio, and wherein molar ratio shared by maleic anhydride is 0.6-1.5, remaining binary acid
Shared molar ratio is 0-0.9, such as 0.1-0.9, further 0.3-0.9.Optionally, the molar ratio of dihydric alcohol and binary acid
For 1:1.15-1.35, wherein molar ratio shared by maleic anhydride is 0.6-1.35, molar ratio shared by remaining binary acid
For 0.15-0.9.
Further, intermediate described in step (3) accounts for the 20-40% of intermediate and reactant A gross mass, such as 20-
30% or 30-40%.
Further, promotor described in step (4) be cobalt iso-octoate, isooctyl acid potassium, isooctyl acid copper, copper naphthenate, N,
At least one of accelerine.Optionally, the promotor is cobalt iso-octoate；Optionally, the promotor is different pungent
Sour copper；Optionally, the promotor is n,N-Dimethylaniline；Optionally, the promotor is cobalt iso-octoate and N, N- diformazan
Base aniline；Optionally, the promotor is cobalt iso-octoate, copper naphthenate and n,N-Dimethylaniline.
Further, polymerization inhibitor described in step (4) is methylnaphthohydroquinone, tert-butylhydroquinone, 2,6- di-t-butyl pair
At least one of cresols.Optionally, the polymerization inhibitor is tert-butylhydroquinone；Optionally, the polymerization inhibitor is 2,6- bis-
Butylated Hydroxytoluene；Optionally, the polymerization inhibitor is tert-butylhydroquinone and 2,6-di-tert-butyl p-cresol, such as mass ratio
For 1:0.8-1.2.
A kind of preparation method of the soybean oil modified unsaturated polyester resin according to is prepared soybean oil modified
Unsaturated polyester resin is tested according to GB/T 2567-2008, its tensile strength is 35-50MPa after solidification, is had no progeny and is prolonged
Stretching rate is 7-15%, bending strength 50-80MPa, and cubical contraction is 4-7% after solidification, and resin pours building body with good
Surface drying performance, after normal cure 2-4h can surface drying, the collocation for passing through suitable promotor and polymerization inhibitor uses, the storage of resin
It deposits stability and surface drying is obviously improved.Elongation after fracture and nothing relative to common unsaturated polyester resin 1.5-8%
The characteristics of wax pattern unsaturated polyester resin is difficult from surface drying, the present invention have obvious special excellent properties.
Compared with the existing technology, beneficial effects of the present invention:
(1) soybean oil has successfully been made as main material with reproducible, environmental-friendly soybean oil in present invention selection
Modified unsaturated polyester resin；Good mechanical properties after solidification, good toughness, cure shrinkage are smaller；Have after its resin solidification
It is certain to save the step of traditional unsaturated polyester resin needs to add the surface drying auxiliary agent of paraffin from surface drying ability, and the later period adds
Work does not have to carry out polishing again to remove wax；
(2) compared to the elongation after fracture from empty dry dicyclic pentylene modified unsaturated polyester resin 2% or so, originally
Invention elongation after fracture is obviously much bigger.
(3) relative to the unsaturated polyester resin formula that other use epoxidized soybean oil modified, the present invention is directly used greatly
Soya-bean oil is produced, and raw material is easy to obtain, and not having to any purifying can be used, and cheap, low energy consumption；
(4) synthetic route that soybean oil is introduced unsaturated polyester resin by the present invention is simple and easy, and tradition can be used not
Saturated polyester equipment is produced, and is easy to realize industrial production；
(5) for soybean oil as biomass material, abundance is cheap, and soybean oil is introduced unsaturated polyester resin
Formula in advantageously reduce the consumption of petrochemical material, improve the added value of soybean, also comply with energy-saving and emission-reduction and sustainable development
Development strategy.
Specific embodiment
In order to preferably explain the present invention, it is described further now in conjunction with following specific embodiments, but the present invention is unlimited
In specific embodiment.
Embodiment 1
A kind of preparation method of soybean oil modified unsaturated polyester resin, comprising the following steps:
(1) it by 130 portions of soybean oils, 72 parts of diglycols and 0.06 part of dibutyl tin dilaurate, throws to reaction kettle
Middle stirring is warming up to 220 DEG C, keeps the temperature 2-3h, obtains intermediate；Judge whether gained intermediate meets the requirements: by the sample after heat preservation
Product sample and sample and ethyl alcohol are uniformly dispersed according to mass ratio 1:1, are cooled to 25 DEG C, observation sample and ethyl alcohol aggregate sample are clarified
It is transparent to reach terminal；
(2) by the adjacent benzene two of 238 parts of diglycols, 96 parts of 1,2- propylene glycol, 264 parts of maleic anhydrides and 200 parts
Formic anhydride throws into reaction kettle stirring and is warming up to 200 DEG C, and reaction dehydration to system acid value is reduced to 100mgKOH/g or less；
(3) intermediate that reaction obtains in step (1) is added into stirring in step (2) reaction kettle and is warming up to 200 DEG C, constant temperature
Reaction dehydration obtains resin until acid value 25-35mgKOH/g；
(4) 500 parts of styrene are added in dilution kettle, and 0.1 part of tert-butylhydroquinone and 0.05 part of methyl hydrogen is added
Quinone is simultaneously uniformly dispersed, and resin in step (3) is then cooled to 130-160 DEG C, slow thinning is into dilution kettle.Control diluted
Dilution temperature is cooled to 45 DEG C hereinafter, addition 1.5 parts of cobalt iso-octoates, 2.5 parts between 55-60 DEG C, after dilution in journey
Isooctyl acid potassium is simultaneously uniformly dispersed to get a kind of soybean oil modified unsaturated polyester resin is arrived.
(5) it is tested according to GB/T 2567-2008, its tensile strength is 48MPa after solidification, and elongation after fracture is
8.5%, bending strength 77MPa, cubical contraction is 6.9% after solidification, and body after the solidification of common unsaturated polyester resin
Product shrinking percentage is in 8% or more (shrink and be unfavorable for using poor dimensional stability greatly)；
The soybean oil modified unsaturated polyester resin of the present embodiment is adding 1.0% methyl ethyl ketone peroxide in 25 DEG C of environment
The thin plate after building up 3-5mm is poured, just there is apparent surface drying after 2.5h, and commonly without wax pattern unsaturated polyester resin substantially without table
It is dry.
Embodiment 2
A kind of preparation method of soybean oil modified unsaturated polyester resin, comprising the following steps:
(1) it by 186 portions of soybean oils, 109 parts of diglycols and 0.10 part of n-BuLi, throws and stirs liter into reaction kettle
Temperature keeps the temperature 2-3h to 220 DEG C, obtains intermediate；Judge whether gained intermediate meets the requirements: by the sample after heat preservation
And sample and ethyl alcohol are uniformly dispersed according to mass ratio 1:1,25 DEG C are cooled to, observing sample with ethyl alcohol aggregate sample clear is
Reach terminal；
(2) by 227 parts of diglycols, 65 parts of 1,2-PDs, 251 parts of maleic anhydrides and 162 parts of tetrahydro neighbours
Phthalate anhydride throws into reaction kettle stirring and is warming up to 205 DEG C, and reaction dehydration to system acid value is reduced to 100mgKOH/g or less；
(3) intermediate that reaction obtains in step (1) is added into stirring in step (2) reaction kettle and is warming up to 205 DEG C, constant temperature
Reaction dehydration obtains resin until acid value is 20-30mgKOH/g；
(4) 500 parts of styrene are added in dilution kettle, and 0.15 part of tert-butylhydroquinone, 0.05 part of methyl hydrogen is added
Quinone, 0.15 part of 2,6-di-tert-butyl p-cresol are simultaneously uniformly dispersed, and resin in step (3) are then cooled to 130-160 DEG C, slowly
Thinning is into dilution kettle.Control dilution in dilution temperature be cooled between 55-60 DEG C, after dilution 45 DEG C with
Under, cobalt iso-octoate, 5 parts of isooctyl acid potassium, 1 part of n,N-Dimethylaniline and the 0.15 part of isooctyl acid copper of 7.5 parts of addition, and disperse equal
It is even to get arrive a kind of soybean oil modified unsaturated polyester resin.
(5) it is tested according to GB/T 2567-2008, its tensile strength is 45MPa after solidification, and elongation after fracture is
12%, bending strength 65MPa, cubical contraction is 6.5% after solidification, and volume after the solidification of common unsaturated polyester resin
Shrinking percentage is 8% or more；
It adds 1.0% methyl ethyl ketone peroxide and pours the thin plate after building up 3-5mm in 25 DEG C of environment, just have after 2h apparent
Surface drying, and commonly without wax pattern unsaturated polyester resin substantially without surface drying；The modified resin of the present embodiment is when 80 DEG C of baking ovens store
Between > 72h.
Embodiment 3
A kind of preparation method of soybean oil modified unsaturated polyester resin, comprising the following steps:
(1) it by 247 portions of soybean oils, 127 parts of diglycols and 0.12 part of dibutyl tin dilaurate, throws to reaction kettle
Middle stirring is warming up to 220 DEG C, and keeps the temperature 2-3h, obtains intermediate；Judge whether gained intermediate meets the requirements: after heat preservation
Sample and ethyl alcohol are simultaneously uniformly dispersed by sample according to mass ratio 1:1, are cooled to 25 DEG C, observe sample and ethyl alcohol aggregate sample is clear
It is clear bright to reach terminal.
(2) by 181 parts of diglycols, 65 parts of 1,2-PDs, 250 parts of maleic anhydrides and 130 parts of tetrahydro neighbours
Phthalate anhydride throws into reaction kettle stirring and is warming up to 205 DEG C, and reaction dehydration to system acid value is reduced to 100mgKOH/g or less.
(3) intermediate that reaction obtains in step (1) is added into stirring in step (2) reaction kettle and is warming up to 205 DEG C, constant temperature
Reaction dehydration obtains resin until acid value is 20-30mgKOH/g.
(4) 500 parts of styrene are added in dilution kettle, and 0.15 part of tert-butylhydroquinone, 0.05 part of methyl hydrogen is added
Quinone, 0.15 part of 2,6-di-tert-butyl p-cresol are simultaneously uniformly dispersed, and resin in step (3) are then cooled to 130-160 DEG C, slowly
Thinning is into dilution kettle.Control dilution in dilution temperature be cooled between 55-60 DEG C, after dilution 45 DEG C with
Under, cobalt iso-octoate, 5 parts of isooctyl acid potassium, 1 part of n,N-Dimethylaniline and the 0.15 part of isooctyl acid copper of 7.5 parts of addition simultaneously disperse equal
It is even to get arrive a kind of soybean oil modified unsaturated polyester resin.
(5) it is tested according to GB/T 2567-2008, its tensile strength is 42MPa after solidification, and elongation after fracture is
14%, bending strength 55MPa, cubical contraction is 5.5% after solidification, and volume after the solidification of common unsaturated polyester resin
Shrinking percentage is 8% or more；
It adds 1.0% methyl ethyl ketone peroxide and pours the thin plate after building up 3-5mm in 25 DEG C of environment, just have after 1.5h obvious
Surface drying, and commonly without wax pattern unsaturated polyester resin substantially without surface drying；The modified resin of the present embodiment is stored in 80 DEG C of baking ovens
Time > 72h.
Comparative example 1
A kind of preparation method of soybean oil modified unsaturated polyester resin, process is same as Example 1, the difference is that
With Mono-n-butyltin instead of dibutyl tin dilaurate, modified resin is made.Observing response is wherein sampled in step (1)
When terminal, the just basic clarification after 220 DEG C of constant temperature 7h is needed, is taken long time.
Tested according to GB/T 2567-2008, after solidification its tensile strength be 30MPa, elongation after fracture 8.6%,
Bending strength is 67MPa, and cubical contraction is 7.0% after solidification；It adds 1.0% curing agent and is poured in 25 DEG C of environment and build up 3-
Thin plate after 5mm just has apparent surface drying after 4.5h, and compared with Example 1, this comparative example resin intensity and surface drying time are equal
It decreased significantly.
Comparative example 2
A kind of preparation method of soybean oil modified unsaturated polyester resin, process is same as Example 2, the difference is that
With 0.35 part of hydroquinone instead of in embodiment 2 polymerization inhibitor (0.15 part of tert-butylhydroquinone, 0.05 part of hydroquinone,
0.15 part of 2,6-di-tert-butyl p-cresol), modified resin is made.
It is tested according to GB/T 2567-2008, the modified resin of this comparative example is reduced in 80 DEG C of baking oven storage times
48h, storage time is decreased obviously compared with Example 2.
Comparative example 3
A kind of preparation method of soybean oil modified unsaturated polyester resin, process is same as Example 3, the difference is that
With 13.65 parts of cobalt naphthenates instead of promotor (7.5 parts of the cobalt iso-octoate, 5 parts of isooctyl acid potassium, 1 part of N, N- in embodiment 3
Dimethylaniline and 0.15 part of isooctyl acid copper), modified resin is made.
It is tested according to GB/T 2567-2008, the modified resin of this comparative example pours body surface drying time and is extended for 3.8h
More than, 80 DEG C of baking oven storage times are also reduced by 50h.
Above is only a specific embodiment of the present invention, it is not intended to limit the scope of the invention, all utilizations
The equivalent transformation that the present invention makees, is applied directly or indirectly in other relevant technical fields, similarly includes of the invention
Among scope of patent protection.
Claims (10)
1. a kind of preparation method of soybean oil modified unsaturated polyester resin, which comprises the following steps:
(1) soybean oil, dihydric alcohol, catalyst are added to stirring in reaction kettle and are warming up to 200-240 DEG C, and keep the temperature 2-4h, obtained
To intermediate；The molar ratio of dihydric alcohol and soybean oil is 3.0-7.0:1, and the catalyst accounts for soybean oil and dihydric alcohol gross mass
0.01-0.10%；
(2) by dihydric alcohol, binary acid, 1:1.1-1.5 is added in reaction kettle stirring and is warming up to 190-210 DEG C in molar ratio, reaction
Dehydration is to system acid value to 100mgKOH/g hereinafter, reactant A is obtained, wherein the binary acid includes at least maleic anhydride；
(3) intermediate described in step (1) is added in the reactant A of step (2), stirring is warming up to 190-210 DEG C, obtains
Resin；
(4) resin described in step (3) is cooled to 130-160 DEG C, is mixed with polymerization inhibitor, styrene, control temperature in 55-70
Between DEG C, 45 DEG C are cooled to hereinafter, addition promotor inhibits wherein the mass ratio of the styrene and resin is 0.2-0.8:1
The amount of agent is the 50-350ppm of styrene and resin gross mass, and the amount of promotor is polymerization inhibitor, styrene and resin gross mass
0.2-2%.
2. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that described two
First alcohol is ethylene glycol, 1,2- propylene glycol, diglycol, 2- methyl-1,3-propanediol, 1,4- butanediol, 2,2- dimethyl-
At least one of 1,3- propylene glycol.
3. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that step
(1) molar ratio of dihydric alcohol and soybean oil described in is 3.9-6.0:1；Dihydric alcohol described in step (2) and binary acid
Molar ratio is 1:1.15-1.35；The mass ratio of styrene described in step (4) and resin is 0.4-0.6:1.
4. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that described to urge
Agent is at least one of dibutyl tin dilaurate, certain herbaceous plants with big flowers acid lithium, lithium titanate, n-BuLi.
5. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that step
(3) intermediate described in accounts for the 20-40% of intermediate and reactant A gross mass.
6. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that described two
First acid further include phthalic anhydride, tetrabydrophthalic anhydride, terephthalic acid (TPA), M-phthalic acid, in hexahydrophthalic anhydride extremely
Few one kind.
7. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that step
(2) molar ratio shared by maleic anhydride described in is 0.6-1.5.
8. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that step
(4) promotor described in is cobalt iso-octoate, isooctyl acid potassium, isooctyl acid copper, copper naphthenate, N, at least one in accelerine
Kind.
9. the preparation method of soybean oil modified unsaturated polyester resin according to claim 1, which is characterized in that step
(4) polymerization inhibitor described in is at least one of methylnaphthohydroquinone, tert-butylhydroquinone, DBPC 2,6 ditertiary butyl p cresol.
10. a kind of preparation method system of soybean oil modified unsaturated polyester resin according to claim 1 to 9
Standby obtained soybean oil modified unsaturated polyester resin.
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| CN201811251595.2A CN109337054A (en) | 2018-10-25 | 2018-10-25 | Soybean oil modified unsaturated polyester resin and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751669A (en) * | 2022-03-24 | 2022-07-15 | 华南农业大学 | Unsaturated polyester resin accelerator and preparation method and application thereof |
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| JP2009292858A (en) * | 2008-06-02 | 2009-12-17 | Showa Highpolymer Co Ltd | Method for producing unsaturated polyester, unsaturated polyester resin composition and unsaturated polyester resin cured molded article |
| CN105505152A (en) * | 2016-02-02 | 2016-04-20 | 嘉兴市嘉盛绝缘材料有限公司 | Soybean oil modified unsaturated polyester impregnating varnish and preparation method thereof |
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2018
- 2018-10-25 CN CN201811251595.2A patent/CN109337054A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009292858A (en) * | 2008-06-02 | 2009-12-17 | Showa Highpolymer Co Ltd | Method for producing unsaturated polyester, unsaturated polyester resin composition and unsaturated polyester resin cured molded article |
| CN105505152A (en) * | 2016-02-02 | 2016-04-20 | 嘉兴市嘉盛绝缘材料有限公司 | Soybean oil modified unsaturated polyester impregnating varnish and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| FEREIDOON SHAHIDI: "《贝雷油脂化学与工艺学 第六版 第六卷 油脂的工业产品与非食用产品》", 31 December 2016, 中国轻工业出版社 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114751669A (en) * | 2022-03-24 | 2022-07-15 | 华南农业大学 | Unsaturated polyester resin accelerator and preparation method and application thereof |
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