CN109734890A - A kind of preparation method of no styrene unsaturated-resin - Google Patents
A kind of preparation method of no styrene unsaturated-resin Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of no styrene unsaturated-resin, monohydric alcohol, polyalcohol, monoacid/acid anhydride, saturated polybasic acid/acid anhydride and/or unsaturated polyacid/acid anhydride melt polymerization are saturated or unsaturated polyester (UP)；(methyl) glycidyl acrylate is uniformly mixed with saturation or unsaturated polyester (UP), and under the effect of the catalyst, opening obtains unsaturated-resin；Unsaturated-resin, reactive diluent and polymerization inhibitor are mixed to prepare no styrene unsaturated-resin.No styrene unsaturated-resin synthetic route of the present invention prepared by the present invention is simple and convenient, and modest viscosity, wellability are good, it is good to adhere to base material, meets different process demand；Being air-dried property of product surface is good, energy rapid curing, excellent comprehensive mechanical property, and operability is good；Low VOC, discharge environmental protection can be widely applied to the fields such as building, house ornamentation covering with paint, traffic car and boat inside gadget and component of machine；Belong to general chemicals simultaneously, is conducive to logistics transportation.
Description
Technical field
The present invention relates to field of polymer composite material more particularly to a kind of preparation sides of no styrene unsaturated-resin
Method.
Background technique
It is well known that unsaturated resin products are widely used in the wind-powered electricity generation energy, rail traffic, lightweight engineering, environmentally friendly work
The national economy fields such as journey, energy saving building, house ornamentation covering with paint, greatly facilitate the daily life of the people.It is produced for final
The performance and price factor of product comprehensively consider, and general unsaturated-resin, as diluent, accounts for about 20-50% using styrene.But
Styrene flash-point is low, volatile, and the most key is that styrene has strong impulse and anesthetic effect, and potential cause
The denaturation of carcinous and teratogenesis, is classified as the dangerous substance of priority, each state is all to yard by the Environmental Protection Agency of Main Countries
Concentration of styrene limit.In addition, to the VOC emission control of closing and the terminal applies place such as semiclosed also at
For key subjects, and have neither part nor lot in the important sources that cured styrene is exactly VOC.Resins with low styrene emission resin (low benzene second
Alkene content resin, the resin of volatilization inhibitor containing styrene) it not can solve styrene and discharge this problem, and low-styrene is waved
Hair resin system role under compared with high environment temperature (40 DEG C of summer or more) is limited.It thus develops and promotes and is low
Volatilization styrene even has become mainstream demand instantly and prior development direction without styrene resin.West Main Developed Countries
It is widely used no styrene resin, also there are more related patents to be reported.More it is typically John
The patent for the related no styrene unsaturated polyester resin that E.McAlvin et al. is delivered, their design scheme mainly includes four
Kind key component: a kind of unsaturated polyester (UP) (predominantly vinyl esters, the unsaturated polyester (UP) that DCPD replaces), a kind of urethane acrylic acid
Ester, a kind of acrylate monomer (HEMA, HPMA) that hydroxyl replaces, a kind of multi-functional acrylate.They have found some
The performance of formula can reach or even surmount the Solidified enzyme of unsaturated polyester resin containing styrene, it is seen that urethane acrylate
The raising of resin property is played a crucial role in conjunction with multi-functional acrylate, but program complicated components, and
Not the problem of not referring to being air-dried property of resin.JP2002332316A then discloses a kind of no styrene resin, uses
Hydroxyalkyl methacrylate is as reactive diluent, although the resin solidification, safety and surface drying excellent, are deposited
In the problem inadequate with base material adhesive force.CN105622858A discloses the acrylate using not volatile, low smell
Class monomer substitutes styrene, and the unsaturated polyester (UP) modified with crylic acid hydroxy ester and isocyanate block copolymerization mixes, and constitutes nothing
The bulk composition of styrene resin, but that there are steps is complicated, isocyanates toxicity is big, block polymerization modification unsaturated polyester (UP) molecule
Measure big disadvantage.Therefore, it is necessary to develop the technology path of novel no styrene resin preparation, meet low VOC emission, comprehensive mechanics
The requirement that performance is good, route is simple and convenient, good with base material good attachment, being air-dried property.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies of existing technologies, a kind of preparation side of no styrene unsaturated-resin is provided
Method.
Realizing the technical solution of the object of the invention is: a kind of preparation method of no styrene unsaturated-resin, the preparation
Method includes the following steps,
(1) monohydric alcohol, polyalcohol, monoacid/acid anhydride, saturated polybasic acid/acid anhydride and/or unsaturated polyacid/acid anhydride are melted poly-
It closes, is saturated or unsaturated polyester (UP)；
(2) glycidyl methacrylate or glycidyl acrylate mix with the saturation or unsaturated polyester (UP)
Even, under the effect of the catalyst, opening obtains unsaturated-resin；
(3) unsaturated-resin, reactive diluent and polymerization inhibitor are mixed to prepare the no styrene unsaturated-resin.
Monohydric alcohol described in above-mentioned technical proposal be n-butanol, 1- octanol, 3-Methoxy-3-methyl-1-butanol, neopentyl alcohol,
Benzyl alcohol, benzyl carbinol, cyclohexanol, 3- cyclohexene -1- methanol, cinnamyl alcohol, ethylene glycol monoallyl ether, trimethylolpropane diene
One of propyl ether and its derivative are a variety of；
The polyalcohol is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, methyl propanediol, 2- fourth
Base -2- ethyl -1,3- propylene glycol, 1,4- butanediol, 1,3 butylene glycol, neopentyl glycol, 2,2,4- trimethyl -1,3- pentanediol,
Hexylene glycol, 1,4 cyclohexane dimethanol, hydrogenated bisphenol A, 3- hydroxyl -2,2- neopentanoic acid (3- hydroxyl -2,2- dimethyl propylene
Base) ester, trimethylolpropane and one of triethylol propane and its derivative or a variety of；
Monoacid/the acid anhydride is acetic anhydride, butyric acid, caproic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid, benzoic acid, linolein
One of fat acid, behenic acid, ready denier oil acid, eleostearic acid, dehydrated castor oleic acid and its derivative are a variety of；
Saturated polybasic acid/the acid anhydride be ethanedioic acid, succinic acid, adipic acid, cyclohexane diacid, suberic acid, decanedioic acid, phthalic anhydride,
M-phthalic acid, terephthalic acid (TPA), hexahydrophthalic anhydride, 1,4 cyclohexanedicarboxylic acid, dimeric dibasic acid, preference degrees and Pyromellitic Acid
And its one of derivative or a variety of；
Unsaturation polyacid/the acid anhydride is maleic anhydride, maleic acid, fumaric acid, itaconic acid, mesaconic acid, lemon
Health acid, citraconic anhydride, tetrahydrophthalic anhydride, carbic anhydride, carbic acid, methyl -5- norbornene -2,3- dicarboxylic acids
Acid anhydride, methyl -5- norbornene -2,3- dicarboxylic acids, aconitic acid and one of cis-aconitic anhydride and its derivative or a variety of.
Reactive diluent described in above-mentioned technical proposal is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, methacrylic acid
Hydroxypropyl acrylate, hydroxypropyl acrylate, glycol diacrylate, 1,4 butanediol diacrylate, 1,6-HD diacrylate
Ester, tri (propylene glycol) diacrylate, dipropylene glycol diacrylate, trimethylolpropane trimethacrylate, acetoacetate
Amino ethyl methacrylate, poly(ethylene glycol) dimethacrylate, diethylene glycol dimethacrylate and glycerol formal third
One of e pioic acid methyl ester is a variety of.
Catalyst described in above-mentioned technical proposal is one of amine, triphenylphosphine or a variety of.
Amine described in above-mentioned technical proposal is N, N- dimethyl benzylamine, N, N- diethyl benzylamine, ethylenediamine, triethylamine, three
Ethanol amine, N, one of N- dimethylethanolamine or a variety of.
Polymerization inhibitor described in above-mentioned technical proposal is copper naphthenate, methylnaphthohydroquinone, copper di-n-butyldithiocarbamate, right
Benzenediol, phenol, p methoxy phenol, p-methyl phenol, p-tert-Butylcatechol, 2,6 di tert butyl 4 methyl phenol,
One or more of benzoquinones, tetramethyl piperidine nitrogen oxides and its derivative.
The dosage of monohydric alcohol described in above-mentioned technical proposal is 1.5-15 parts by weight；The dosage of the polyalcohol is 1-20 weight
Part；The dosage of the monoacid/acid anhydride is 0-10 parts by weight；The use of the saturated polybasic acid/acid anhydride and/or unsaturated polyacid/acid anhydride
Amount is 1-30 parts by weight；Glycidyl methacrylate or the dosage of glycidyl acrylate are 5-20 parts by weight；It is described
The dosage of catalyst is 0.001-0.5 parts by weight；The dosage of the reactive diluent is 20-70 parts by weight；The polymerization inhibitor
Dosage is 0.0001-0.1 parts by weight.
In step described in above-mentioned technical proposal (1), by the monohydric alcohol and the polyalcohol heating melting, then successively with
Monoacid/the acid anhydride, the saturated polybasic acid/acid anhydride and/or unsaturated polyacid/acid anhydride, carry out polymerization reaction；The heating melting
It is carried out under an inert atmosphere with the polymerization reaction, the inert atmosphere can be the inert atmosphere of this field routine, such as nitrogen
Atmosphere；The temperature of the polymerization reaction is 90-230 DEG C.
In step described in above-mentioned technical proposal (2), the opening carries out under atmosphere of inert gases, described lazy
Property atmosphere can be this field routine inert atmosphere, such as nitrogen atmosphere；The opening temperature is 80-135 DEG C；Institute
It states opening and reacts to acid value and reach 1-50 mgKOH/g.
In step described in above-mentioned technical proposal (3), mixed temperature is 40-80 DEG C.
After adopting the above technical scheme, the present invention have the effect of it is following positive:
(1) synthetic route of the present invention is simple and convenient, using glycidyl methacrylate or glycidyl acrylate
Air drying type saturation or unsaturated polyester (UP) are modified, esters of acrylic acid double bond is introduced in strand, can be significantly improved not
The copolymerized characteristic of saturated polyester and esters of acrylic acid reactive diluent, meanwhile, tune while not significantly increasing molecular weight of polyesters
Save molecular polarity, make to be prepared without styrene unsaturated-resin have modest viscosity, with glass wellability it is good, with substrate material
Material adheres to good feature, can satisfy different construction technology demands, the especially moulding process such as hand paste, injection.
(2) no being air-dried property of styrene unsaturated-resin product surface of the invention is good, can rapid curing, integrated machine
Tool is had excellent performance, and can realize that equivalent or decrement are substituted with current styrene type unsaturated polyester resin, construction technology is consistent, behaviour
The property made is more preferably.
(3) the reactive diluent boiling point that no styrene unsaturated-resin of the invention is selected is much higher than styrene, and smell
It is low, have the characteristics that ordor removing, low VOC, discharge environmental protection, can be widely applied to building, house ornamentation covering with paint, bathroom, rail traffic, vapour
The fields such as vehicle, ship inside gadget and component of machine；Belong to general chemicals simultaneously, is conducive to logistics transportation.
Detailed description of the invention
In order that the present invention can be more clearly and readily understood, right below according to specific embodiment and in conjunction with attached drawing
The present invention is described in further detail, wherein
Fig. 1 is the static volatilization comparison diagram of product of the present invention and common styrene unsaturated-resin.
Specific embodiment
To keep the purpose, technical solution and good effect of the embodiment of the present invention clearer, the present invention will be implemented below
Technical solution in example is clearly and completely described, it is clear that and described embodiments are some of the embodiments of the present invention, and
The embodiment being not all of.
In following embodiments, raw materials used and reagent is all commercially available；Reaction mentioned below can be in this field routine
It carries out in reaction unit, generally carries out in a kettle；Reaction mentioned below carries out under an inert atmosphere, the inert atmosphere
It can be the inert atmosphere of this field routine, such as nitrogen atmosphere.
Embodiment 1
A kind of no styrene unsaturated-resin is prepared by following composition of raw materials and preparation method.
Formula are as follows:
| Concrete component | Weight/g |
| Phthalic anhydride | 30 |
| M-phthalic acid | 20 |
| Tetrahydrophthalic anhydride | 60 |
| 1- octanol | 30 |
| Diethylene glycol | 40 |
| Glycidyl methacrylate | 120 |
| Hydroxyethyl methacrylate | 500 |
| N, N- dimethyl benzylamine | 2 |
| P methoxy phenol | 0.2 |
Steps are as follows for preparation method:
(1) 1- octanol and diethylene glycol are added in the reaction kettle with heat riser and agitating device, open stirring,
Logical nitrogen, is to slowly warm up to 80-85 DEG C, and phthalic anhydride, M-phthalic acid, tetrahydrophthalic anhydride is added, is gradually warming up to 210-215 DEG C, instead
It should be 85-90mgKOH/g to acid value.
(2) it is above-mentioned after reaction, temperature of reaction kettle is adjusted to 110-115 DEG C, catalyst and polymerization inhibitor, Xiang Fanying is added
Glycidyl methacrylate (average to be added in three times) is added in kettle, control kettle temperature adds at 110-120 DEG C during charging
It is reacted after complete at 115-120 DEG C, reacts to the acid value of reaction system and reach 3.0-5.0mgKOH/g.
(3) aforesaid reaction vessel temperature is down to 60-70 DEG C, hydroxyethyl methacrylate and remaining polymerization inhibitor is added, stirs
It mixes and is uniformly mixed.
Embodiment 2
A kind of no styrene unsaturated-resin is prepared by following composition of raw materials and preparation method.
Formula are as follows:
| Concrete component | Weight/g |
| Maleic anhydride | 80 |
| Benzoic acid | 40 |
| Trimethylolpropane allyl ether | 80 |
| 1,4- butanediol | 60 |
| Glycidyl acrylate | 60 |
| Tri (propylene glycol) diacrylate | 260 |
| 1,6 hexanediol diacrylate | 220 |
| Triphenylphosphine | 1.8 |
| Methylnaphthohydroquinone | 0.3 |
| Copper naphthenate | 0.1 |
Steps are as follows for preparation method:
(1) trimethylolpropane allyl ether and 1,4- butanediol are added to heat riser and agitating device
In reaction kettle, stirring is opened, leads to nitrogen, is to slowly warm up to 80-85 DEG C, maleic anhydride, benzoic acid is added, is gradually warming up to
160-170 DEG C, reaction to acid value is 52-60mgKOH/g.
(2) it is above-mentioned after reaction, temperature of reaction kettle is adjusted to 90-95 DEG C, catalyst and polymerization inhibitor is added, to reaction kettle
Interior addition glycidyl acrylate (average to be added in three times), during charging control kettle temperature at 90-105 DEG C, after adding
100-105 DEG C of reaction reacts to the acid value of reaction system and reaches 5.0-10.0mgKOH/g.
(3) aforesaid reaction vessel temperature is down to 50-60 DEG C, hydroxyethyl methacrylate and remaining polymerization inhibitor is added, stirs
It mixes and is uniformly mixed.
Embodiment 3
A kind of no styrene unsaturated-resin is prepared by following composition of raw materials and preparation method.
Formula are as follows:
| Concrete component | Weight/g |
| Phthalic anhydride | 160 |
| Ethylene glycol monoallyl ether | 80 |
| Propylene glycol | 10 |
| Neopentyl glycol | 10 |
| Glycidyl methacrylate | 140 |
| Glycerol formal methyl acrylate | 200 |
| Hydroxy propyl methacrylate | 200 |
| N, N- dimethyl benzylamine | 2.0 |
| P-tert-Butylcatechol | 0.1 |
| 2,6- di-tert-butyl methyl phenol | 0.2 |
Steps are as follows for preparation method:
(1) ethylene glycol monoallyl ether, propylene glycol and neopentyl glycol are added to heat riser and agitating device
In reaction kettle, stirring is opened, leads to nitrogen, is to slowly warm up to 80-85 DEG C, phthalic anhydride is added, is gradually warming up to 160-170 DEG C, reaction
It is 205-210mgKOH/g to acid value.
(2) it is above-mentioned after reaction, temperature of reaction kettle is adjusted to 90-95 DEG C, catalyst and polymerization inhibitor is added, to reaction kettle
Interior addition glycidyl methacrylate (average to be added in three times), control kettle temperature is added at 90-105 DEG C during charging
It is reacted afterwards at 100-105 DEG C, reacts to the acid value of reaction system and reach 20.0-25.0mgKOH/g.
(3) aforesaid reaction vessel temperature is down to 50-55 DEG C, hydroxyethyl methacrylate and remaining polymerization inhibitor is added, stirs
It mixes and is uniformly mixed.
Embodiment 4
A kind of no styrene ethylene base ester resin is prepared by following composition of raw materials and preparation method.
Formula are as follows:
| Concrete component | Weight/g |
| Fumaric acid | 220 |
| Benzyl alcohol | 100 |
| Hexylene glycol | 140 |
| Glycidyl acrylate | 40 |
| Dipropylene glycol diacrylate | 100 |
| Trimethylolpropane trimethacrylate | 100 |
| N, N- dimethyl benzylamine | 1.0 |
| P-tert-Butylcatechol | 0.07 |
| 2,6- di-tert-butyl methyl phenol | 0.1 |
Steps are as follows for preparation method:
(1) benzyl alcohol, 1,6- hexylene glycol are added in the reaction kettle with heat riser and agitating device, unlatching is stirred
It mixes, leads to nitrogen, be to slowly warm up to 80-85 DEG C, fumaric acid is added, be gradually warming up to 200-205 DEG C, reaction to acid value is 80-
85mgKOH/g。
(2) it is above-mentioned after reaction, temperature of reaction kettle is adjusted to 90-100 DEG C, catalyst and polymerization inhibitor, Xiang Fanying is added
Glycidyl acrylate is added in kettle, control kettle temperature is anti-at 115-125 DEG C after adding at 100-120 DEG C during charging
It answers, reacts to the acid value of reaction system and reach 40.0-45.0mgKOH/g.
(3) aforesaid reaction vessel temperature is down to 40-45 DEG C, hydroxyethyl methacrylate and remaining polymerization inhibitor is added, stirs
It mixes and is uniformly mixed.
Effect example 1
Physical property measurement is carried out without styrene unsaturated-resin to made from 1-4 of the embodiment of the present invention, specific test result is such as
Shown in following table.
Effect example 2
Without 0.2% promotor 6%Co- is added in styrene ethylene base ester resin made from the 1-4 of the embodiment of the present invention
Naph and 2% curing agent AKZO M-50, casting matrix method for making sample are executed by GB/T8237, and specific test result is as follows shown in table.
As seen from the above table, using having excellent comprehensive mechanical after the solidifying without styrene unsaturated-resin of embodiment 1-4
Performance.It is well known that the oxygen inhibition ability of acrylic ester monomer is stronger, using embodiment 1-4 without styrene unsaturation tree
It is dry that product surface can be realized after rouge room temperature curing, be not required to high temperature post cure processing.In addition, can be got in 1h after solidification
Hardness Barcol, while heat release is no more than 180 DEG C in cup.Illustrate that curing rate is fast, heat release is low, and working efficiency can be improved.
Effect example 3
It will be uniformly mixed made from 1-4 of the embodiment of the present invention without styrene unsaturated-resin equal proportion, in 25 DEG C of environment temperature
Degree is lower and common styrene type unsaturated-resin carries out static volatility and compares, and specific test result is as follows shown in Fig. 1.
Due to the substituted type reactive diluent selected of the present invention have low smell, higher boiling, high-flash characteristic, thus this
The inventive embodiments 1-4 feature obtained that without styrene unsaturated-resin there is ordor removing, low VOC to discharge.This point can be by Fig. 1
Proved: selected common styrene type resin static volatile quantity at 25 DEG C accounts for 2% or so of resin quality, and equal conditions
The static volatile quantity of lower no styrene resin only account for resin quality less than 5/10000ths.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of no styrene unsaturated-resin, which is characterized in that the preparation method includes the following steps:
(1) it by monohydric alcohol, polyalcohol, monoacid/acid anhydride, saturated polybasic acid/acid anhydride and/or unsaturated polyacid/acid anhydride melt polymerization, obtains
To saturation or unsaturated polyester (UP)；
(2) glycidyl methacrylate or glycidyl acrylate are uniformly mixed with the saturation or unsaturated polyester (UP),
Under the effect of the catalyst, opening obtains unsaturated-resin；
(3) unsaturated-resin, reactive diluent and polymerization inhibitor are mixed to prepare the no styrene unsaturated-resin.
2. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: the unitary
Alcohol is n-butanol, 1- octanol, 3-Methoxy-3-methyl-1-butanol, neopentyl alcohol, benzyl alcohol, benzyl carbinol, cyclohexanol, 3- hexamethylene
One of alkene -1- methanol, cinnamyl alcohol, ethylene glycol monoallyl ether, trimethylolpropane allyl ether and its derivative or
It is a variety of；
The polyalcohol is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, methyl propanediol, 2- butyl -2-
Ethyl -1,3- propylene glycol, 1,4- butanediol, 1,3 butylene glycol, neopentyl glycol, 2,2,4- trimethyl -1,3- pentanediol, oneself two
Alcohol, 1,4 cyclohexane dimethanol, hydrogenated bisphenol A, 3- hydroxyl -2,2- neopentanoic acid (3- hydroxyl -2,2- dimethyl propyl) ester,
Trimethylolpropane and one of triethylol propane and its derivative are a variety of；
Monoacid/the acid anhydride is acetic anhydride, butyric acid, caproic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid, benzoic acid, linseed oil fat
One of acid, behenic acid, ready denier oil acid, eleostearic acid, dehydrated castor oleic acid and its derivative are a variety of；
Saturated polybasic acid/the acid anhydride is ethanedioic acid, succinic acid, adipic acid, cyclohexane diacid, suberic acid, decanedioic acid, phthalic anhydride, isophthalic
Dioctyl phthalate, terephthalic acid (TPA), hexahydrophthalic anhydride, 1,4 cyclohexanedicarboxylic acid, dimeric dibasic acid, preference degrees and Pyromellitic Acid and its
One of derivative is a variety of；
It is described unsaturation polyacid/acid anhydride be maleic anhydride, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid,
Citraconic anhydride, tetrahydrophthalic anhydride, carbic anhydride, carbic acid, methyl -5- norbornene -2,3- dicarboxylic anhydride, first
Base -5- norbornene -2,3- dicarboxylic acids, aconitic acid and one of cis-aconitic anhydride and its derivative or a variety of.
3. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: the activity
Diluent is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, ethylene glycol two
Acrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, tri (propylene glycol) diacrylate, two
Propylene glycol diacrylate, trimethylolpropane trimethacrylate, acetoacetoxyethyl methacrylate, dimethacrylate
One of macrogol ester, diethylene glycol dimethacrylate and glycerol formal methyl acrylate are a variety of.
4. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: the catalysis
Agent is one of amine, triphenylphosphine or a variety of.
5. a kind of preparation method of no styrene unsaturated-resin according to claim 4, it is characterised in that: the amine
For N, N- dimethyl benzylamine, N, N- diethyl benzylamine, ethylenediamine, triethylamine, triethanolamine, N, one in N- dimethylethanolamine
Kind is a variety of.
6. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: the polymerization inhibitor
Agent is copper naphthenate, methylnaphthohydroquinone, copper di-n-butyldithiocarbamate, hydroquinone, phenol, p methoxy phenol, right
Methylphenol, p-tert-Butylcatechol, 2,6 di tert butyl 4 methyl phenol, benzoquinones, tetramethyl piperidine nitrogen oxides and its
One or more of derivative.
7. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: the unitary
The dosage of alcohol is 1.5-15 parts by weight；The dosage of the polyalcohol is 1-20 parts by weight；The dosage of the monoacid/acid anhydride is 0-10
Parts by weight；The dosage of the saturated polybasic acid/acid anhydride and/or unsaturated polyacid/acid anhydride is 1-30 parts by weight；Glycidyl methacrylate
The dosage of glyceride or glycidyl acrylate is 5-20 parts by weight；The dosage of the catalyst is 0.001-0.5 parts by weight；
The dosage of the reactive diluent is 20-70 parts by weight；The dosage of the polymerization inhibitor is 0.0001-0.1 parts by weight.
8. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: step (1)
In, by the monohydric alcohol and the polyalcohol heating melting, then successively with the monoacid/acid anhydride, the saturated polybasic acid/acid anhydride
And/or unsaturated polyacid/acid anhydride, carry out polymerization reaction；The heating melting and the polymerization reaction carry out under an inert atmosphere；
The temperature of the polymerization reaction is 90-230 DEG C.
9. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: step (2)
In, the opening carries out under atmosphere of inert gases；The opening temperature is 80-135 DEG C；It is described to open
Cycloaddition reaction reacts to acid value and reaches 1-50mgKOH/g.
10. a kind of preparation method of no styrene unsaturated-resin according to claim 1, it is characterised in that: step (3)
In, mixed temperature is 40-80 DEG C.
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| CN110591010A (en) * | 2019-08-28 | 2019-12-20 | 广东晨宝复合材料有限公司 | Water-resistant styrene-free artificial stone resin and preparation method thereof |
| CN110591010B (en) * | 2019-08-28 | 2022-03-15 | 广东晨宝复合材料有限公司 | Water-resistant styrene-free artificial stone resin and preparation method thereof |
| CN110577804A (en) * | 2019-09-17 | 2019-12-17 | 湖北回天新材料股份有限公司 | Environment-friendly acrylate adhesive with low TVOC (total volatile organic compound) |
| CN112480327A (en) * | 2020-11-19 | 2021-03-12 | 贺州学院 | Method for preparing unsaturated polyester resin by using waste PET (polyethylene terephthalate) product |
| EP4122986A1 (en) * | 2021-07-21 | 2023-01-25 | Ideko, S.Coop. | Ultraviolet resin, composites produced with said resin, and production method thereof |
| CN114316234A (en) * | 2021-12-29 | 2022-04-12 | 常州华科聚合物股份有限公司 | Preparation method of flame-retardant styrene-free hyperbranched unsaturated resin |
| CN114316234B (en) * | 2021-12-29 | 2023-04-07 | 常州华科聚合物股份有限公司 | Preparation method of flame-retardant styrene-free hyperbranched unsaturated resin |
| CN115340669A (en) * | 2022-06-27 | 2022-11-15 | 常州市日新树脂有限公司 | Styrene-free unsaturated polyester resin and preparation method thereof |
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Application publication date: 20190510 |