CN107141420A - Without styrene UPR with low shrinkage resin and preparation method thereof - Google Patents
Without styrene UPR with low shrinkage resin and preparation method thereof Download PDFInfo
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- CN107141420A CN107141420A CN201710418158.4A CN201710418158A CN107141420A CN 107141420 A CN107141420 A CN 107141420A CN 201710418158 A CN201710418158 A CN 201710418158A CN 107141420 A CN107141420 A CN 107141420A
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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
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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
Abstract
The invention discloses one kind without styrene UPR with low shrinkage resin and preparation method thereof, obtained unsaturated polyester resin is applied to compression molding or pultrusion molding process.Contain 60 ~ 75% unsaturated polyester (UP) oligomer, 0.02 ~ 0.05% polymerization inhibitor, 25 ~ 40% diluents, four components of 0.2 2% initiator and 0 ~ 0.5% accelerator.Wherein unsaturated polyester (UP) oligomer is reacted by saturated dicarboxylic acid (acid anhydride), unsaturated dicarboxylic acid (acid anhydride) and saturation dibasic alcohol ester and is made, diluent is the acrylate of alicyclic structure, alternative most popular styrene at present, realize without benzene-like compounds discharge, the cure shrinkage 0.05 ~ 2% of unsaturated polyester resin.The unsaturated polyester resin compositions are applied to compression molding or pultrusion molding process.
Description
Technical field
The present invention relates to one kind without styrene UPR with low shrinkage resin and preparation method thereof, especially it is a kind of not
UPR with low shrinkage resin combination containing styrene, obtained unsaturated polyester resin is applied to compression molding or drawing
Extrusion forming technique.
Background technology
It is extensive because of good, the advantages of curing rate is fast of styrene monomer dilution property since being come out from unsaturated polyester resin
Ground is used as the diluent of unsaturated polyester resin.But in recent years, pay attention to increasingly and state's housekeeping as people are environmentally safe
To the increasingly strict of coating resin industry in plan, using styrene as the application of the unsaturated polyester resin of diluent, because of its smell
And toxicity, increasingly it is restricted, therefore low-styrene or the unsaturated polyester resin without styrene have been developed into the country
The hot subject of outer research and development.
As CN102268167A discloses a kind of preparation method of resins with low styrene emission unsaturated polyester resin composite material,
By adding mesopore molecular sieve in process of production, the hybrid technique of unsaturated polyester resin is adjusted, suppresses unsaturated polyester (UP) tree
Styrene obtains the unsaturated polyester resin composite material of resins with low styrene emission in storage and the volatilization of cure stage in fat.
Dr.Gunter Hegemann are discussed and analyzed with regard to whether styrene in unsaturated polyester (UP) can substitute proposition, and he thinks, from change
Learn angle to set out, styrene can be replaced in unsaturated polyester (UP) by certain comonomer, key is to be substituted with new monomer
During styrene, the performance and economy problems of newly-generated unsaturated polyester resin need to be balanced.JP2002332316A discloses one
The composition of unsaturated polyester resin is planted, it uses hydroxyethyl methacrylate under conditions of curability and physical property is not reduced
Arrcostab substitutes styrene as reactive diluent, although said composition smell is small, curability, security and surface drying
It is excellent, but the problem of presence and the inadequate adhesive force of base material.
In addition, cubical contraction is big when common unsaturated polyester resin solidifies, influence product size and surface smoothness
The application of unsaturated polyester resin Deng, this defective effect, the method for conventional its shrinkage factor of reduction：One kind is by addition
The thermoplastic polymers such as polyethylene, polystyrene are realized, but can not obtain transparent article, and mechanical property dropped
It is low；More than the comparison of another research is the structure of introducing cyclopentadiene in unsaturated polyester resin, and US4228251 is disclosed
The tree that a kind of unsaturated polyester (UP) oligomer of the dicyclic pentylene modified acquisition of hydroxyl and the composition of other components are made
Fat, cured article shrinkage factor is low, flawless.Pass through dicyclic pentylene modified achievable unsaturated polyester resin cure shrinkage
Reduction, but relatively, its synthesis technique is also more complicated than common unsaturated polyester resin.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of unsaturated polyester (UP) without styrene
Resin combination, replaces current the most widely used styrene to be used as dilution using the acrylate of special alicyclic structure
Agent, realizes being discharged without styrene for unsaturated polyester resin.
The technical scheme provided according to the present invention, no styrene UPR with low shrinkage resin is characterized in by saturation
Resin oligomers, polymerization inhibitor, diluent, four components of initiator and accelerator, are made, its structure by Raolical polymerizable
It is as follows：
By unsaturated polyester (UP)
Resin oligomersAs backbone portion,
DiluentIt is used as cross-linked branched part, wherein unsaturated polyester resin
OligomerWeight average molecular weight be 2000~
3000。
The preparation without styrene UPR with low shrinkage resin, step is as follows：
(1) preparation of unsaturated polyester (UP) oligomer：Take saturated dicarboxylic acid/acid anhydride
Unsaturated dicarboxylic acid/acid anhydride and saturation dihydric alcohol (HO-Ra-OH) are according to mol ratio (2.5~7.5):(7.5~2.5):(10.5
~11) feeding, and saturated dicarboxylic acid/acid anhydride and unsaturated dicarboxylic acid/acid anhydride total mole number and saturation dihydric alcohol molal quantity it
Than for 10:(10.5~11)；It is flowed back in 160~175 DEG C of stirring reactions, control vapor (steam) temperature is less than 105 DEG C, tracking and measuring
Acid number gradually rises temperature of reaction system to 190~200 DEG C to 135mgKOH/g, keep the reaction temperature and vacuumize 1~
1.5h, stops heating when reaching 50mgKOH/g to system acid number, produces unsaturated-resin oligomer, structural formula is：
Weight average molecular weight be 2000~
3000。
(2) preparation without styrene UPR with low shrinkage resin：
A, preparation raw material, by mass percentage, including unsaturated polyester (UP) oligomer 60%~75%, polymerization inhibitor 0.02~
0.05%th, diluent 25~40%, initiator 0.2-2% and accelerator 0~0.5%；
When reaction solution obtained by b, step (1) is cooled to 120~140 DEG C, polymerization inhibitor is added, 70~95 DEG C are continued cool to,
Diluent is added, is mixed evenly；
C, addition initiator and accelerator in (b), after stirring, Raolical polymerizables are carried out at 70~90 DEG C,
It is made described without styrene UPR with low shrinkage resin.
Saturated dicarboxylic acid/acid anhydride described in step (1) is phthalic acid, M-phthalic acid, terephthalic acid (TPA), tetrahydrochysene
Change phthalic acid, tetrabydrophthalic anhydride, HHPA, inner methylidyne tetrahydric phthalic anhydride, carbic anhydride, six
One kind in chlorine nadic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, malonic acid, adipic acid or decanedioic acid；Described insatiable hunger
It is one kind in maleic anhydride, maleic acid, fumaric acid, itaconic acid or itaconic anhydride with dicarboxylic acids/acid anhydride；Institute
It is the saturation dihydric alcohol ethylene glycol stated, diethylene glycol (DEG), triethylene glycol, propane diols, dipropylene glycol, tripropylene glycol, butanediol, new
One kind in pentanediol, hexylene glycol, cyclohexanediol or hydrogenated bisphenol A.
Polymerization inhibitor is hydroquinones HQ, adjacent methyl hydroquinone OMHQ, benzoquinones BQ or TBHQ in step (2)
One kind in TBHQ.
Diluent described in step (2) is the acrylate of alicyclic structure, and its skeleton symbol is as follows：
Further, the diluent is specially
In one kind.
Initiator described in step (2) is the compound system of organic peroxide, including two or more initiator
The initiation curing system of composition.
Further, the initiator is specially benzoyl peroxide/dilauroyl peroxide BPO/LPO combinations, peroxide
Change benzoyl/methyl ethyl ketone peroxide/peroxidized t-butyl perbenzoate BPO/MEKP/TBPB combinations, the tertiary fourth of cyclohexanone peroxide/bis-
In base peroxide C YHPO/DTBP combinations or double (2,4 dichloro benzene formyl) BPO/DCBP combinations of benzoyl peroxide/peroxidating
One kind.
By the technical scheme of foregoing invention, obtained unsaturated polyester resin compositions cure shrinkage is low, is applicable to
Compression molding or pultrusion molding process.
Beneficial effects of the present invention：The present invention is used as not using low toxicity, high boiling special cycloaliphatic acrylates monomer
The diluent of saturated polyester resin, can not only realize no styrene discharge, control the discharge of venomous injurant, meet current state
Policy guidance of the family to coating resin class product energy-saving and emission-reduction, it is ensured that the safety in utilization of material, and its special alicyclic ring
Based structures reduce unsaturated polyester resin solidfied material shrinkage factor while keeping unsaturated polyester resin fundamental property constant.
Embodiment
With reference to specific embodiment, the invention will be further described：
Embodiment 1
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1mol phthalic anhydrides are put into mouth glass flask, 1mol maleic anhydrides, 2.2mol propane diols is passed through N2, unlatching stirs
Mix, be warming up to 160~175 DEG C, start backflow, control vapor (steam) temperature be less than 105 DEG C, tracking and measuring acid number to 135mgKOH/g,
Temperature of reaction system is gradually risen to 190~200 DEG C, the reaction temperature is kept and vacuumizes 1~1.5h, reached to system acid number
Stop heating during 50mgKOH/g, produce unsaturated-resin oligomer (LE-1), weight average molecular weight is 3000.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 2
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1.5mol phthalic acids are put into mouth glass flask, 0.5mol maleic acids, 2.1mol ethylene glycol is passed through N2, unlatching stirs
Mix, be warming up to 160~175 DEG C, start backflow, control vapor (steam) temperature be less than 105 DEG C, tracking and measuring acid number to 135mgKOH/g,
Temperature of reaction system is gradually risen to 190~200 DEG C, the reaction temperature is kept and vacuumizes 1~1.5h, reached to system acid number
Stop heating during 50mgKOH/g, produce unsaturated-resin oligomer (LE-2), weight average molecular weight is 2500.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 3
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1.2mol tetrabydrophthalic anhydrides are put into mouth glass flask, 0.8mol fumaric acid, 2.2mol diethylene glycol (DEG)s are passed through N2,
Stirring is opened, 160~175 DEG C are warming up to, starts backflow, control vapor (steam) temperature is less than 105 DEG C, and tracking and measuring acid number is extremely
135mgKOH/g, gradually rises temperature of reaction system to 190~200 DEG C, keeps the reaction temperature and vacuumizes 1~1.5h, extremely
System acid number stops heating when reaching 50mgKOH/g, produces unsaturated-resin oligomer (LE-3), weight average molecular weight is 3000.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 4
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
0.5mol HHPAs are put into mouth glass flask, 1.5mol itaconic anhydrides, 2.2mol dipropylene glycols are passed through N2, open
Stirring, is warming up to 160~175 DEG C, starts backflow, and control vapor (steam) temperature is less than 105 DEG C, tracking and measuring acid number to 135mgKOH/
G, gradually rises temperature of reaction system to 190~200 DEG C, keeps the reaction temperature and vacuumizes 1~1.5h, is reached to system acid number
Stop heating during 50mgKOH/g, produce unsaturated-resin oligomer (LE-4), weight average molecular weight is 2000.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 5
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
0.9mol tetrahydrophthalic acids are put into mouth glass flask, 1.1mol maleic acids, 2.2mol neopentyl glycols are passed through
N2, stirring is opened, 160~175 DEG C are warming up to, starts backflow, control vapor (steam) temperature is less than 105 DEG C, and tracking and measuring acid number is extremely
135mgKOH/g, gradually rises temperature of reaction system to 190~200 DEG C, keeps the reaction temperature and vacuumizes 1~1.5h, extremely
System acid number stops heating when reaching 50mgKOH/g, produces unsaturated-resin oligomer (LE-5), weight average molecular weight is 2500.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 6
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1.5mol inner methylidyne tetrahydric phthalic anhydrides are put into mouth glass flask, 0.5mol maleic anhydrides, 2.12mol tri- is sweet
Alcohol, is passed through N2, stirring is opened, 160~175 DEG C are warming up to, starts backflow, control vapor (steam) temperature is less than 105 DEG C, tracking and measuring acid
Value gradually rises temperature of reaction system to 190~200 DEG C to 135mgKOH/g, keep the reaction temperature and vacuumize 1~
1.5h, stops heating when reaching 50mgKOH/g to system acid number, produces unsaturated-resin oligomer (LE-6), weight average molecular weight is
2000。
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 7
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1.5mol carbic anhydrides are put into mouth glass flask, 0.5mol itaconic anhydrides, 2.2mol butanediols are passed through N2, stirring is opened,
160~175 DEG C are warming up to, starts backflow, control vapor (steam) temperature is less than 105 DEG C, tracking and measuring acid number to 135mgKOH/g, gradually
Temperature of reaction system is raised to 190~200 DEG C, the reaction temperature is kept and vacuumizes 1~1.5h, reached to system acid number
Stop heating during 50mgKOH/g, produce unsaturated-resin oligomer (LE-7), weight average molecular weight is 2500.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 8
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1.4mol M-phthalic acids are put into mouth glass flask, 0.6mol maleic acids, 2.2mol tripropylene glycols are passed through N2,
Stirring is opened, 160~175 DEG C are warming up to, starts backflow, control vapor (steam) temperature is less than 105 DEG C, and tracking and measuring acid number is extremely
135mgKOH/g, gradually rises temperature of reaction system to 190~200 DEG C, keeps the reaction temperature and vacuumizes 1~1.5h, extremely
System acid number stops heating when reaching 50mgKOH/g, produces unsaturated-resin oligomer (LE-8), weight average molecular weight is 2500.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 9
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1mol tetrachlorophthalic tetrachlorophthalic anhydrids are put into mouth glass flask, 1mol maleic anhydrides, 2.2mol cyclohexanediols are passed through N2,
Stirring is opened, 160~175 DEG C are warming up to, starts backflow, control vapor (steam) temperature is less than 105 DEG C, and tracking and measuring acid number is extremely
135mgKOH/g, gradually rises temperature of reaction system to 190~200 DEG C, keeps the reaction temperature and vacuumizes 1~1.5h, extremely
System acid number stops heating when reaching 50mgKOH/g, produces unsaturated-resin oligomer (LE-9), weight average molecular weight is 2000.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
Embodiment 10
(1) preparation of unsaturated polyester (UP) oligomer：Equipped with N2Airway tube, water knockout drum, the four of condenser pipe and agitating device
1mol decanedioic acid is put into mouth glass flask, 1mol fumaric acid, 2.2mol hydrogenated bisphenol As are passed through N2, stirring is opened, is risen
Temperature starts backflow to 160~175 DEG C, and control vapor (steam) temperature is less than 105 DEG C, and tracking and measuring acid number to 135mgKOH/g gradually rises
High temperature of reaction system keeps the reaction temperature and vacuumizes 1~1.5h to 190~200 DEG C, and 50mgKOH/ is reached to system acid number
Stop heating during g, produce unsaturated-resin oligomer (LE-10), weight average molecular weight is 2500.
(2) preparation without styrene UPR with low shrinkage resin：By mass percentage, each raw material, tool are prepared
Body is matched somebody with somebody such as shown in table 1~2.
Terminate preparing unsaturated polyester (UP) oligomer, when being cooled to 120~140 DEG C, add polymerization inhibitor, continue cool to 70
~95 DEG C, diluent is added, is mixed evenly；Initiator and accelerator are added, after stirring, in 70~90 DEG C of progress
Raolical polymerizable, is made without styrene UPR with low shrinkage resin.Specific performance is as shown in table 1~2.
The unsaturated polyester resin each group distribution ratio and performance table of the not be the same as Example of table 1
The unsaturated polyester resin each group distribution ratio and performance table of the not be the same as Example of table 2
Claims (10)
1. without styrene UPR with low shrinkage resin, it is characterized in that by unsaturated-resin oligomer, polymerization inhibitor, dilution
Agent, four components of initiator and accelerator, are made, its structure is as follows by Raolical polymerizable：
By unsaturated polyester resin
OligomerIt is used as backbone portion, dilution
AgentIt is used as cross-linked branched part；Wherein unsaturated polyester resin is oligomeric
ThingWeight average molecular weight be 2000~
3000。
2. the preparation method without styrene UPR with low shrinkage resin described in claim 1, it is characterized in that step is as follows：
(1) preparation of unsaturated polyester (UP) oligomer：Take saturated dicarboxylic acid/acid anhydrideUnsaturation two
First carboxylic acid/anhydride and saturation dihydric alcohol (HO-Ra-OH) are according to mol ratio (2.5~7.5):(7.5~2.5):(10.5~11)
The ratio between feeding, and the total mole number and saturation dihydric alcohol molal quantity of saturated dicarboxylic acid/acid anhydride and unsaturated dicarboxylic acid/acid anhydride
For 10:(10.5~11)；It is flowed back in 160~175 DEG C of stirring reactions, control vapor (steam) temperature is less than 105 DEG C, and tracking is surveyed
Acid number is determined to 135mgKOH/g, temperature of reaction system is gradually risen to 190~200 DEG C, is kept the reaction temperature and is taken out true
1~1.5h of sky, stops heating when reaching 50mgKOH/g to system acid number, produces unsaturated-resin oligomer, structural formula is：Weight average molecular weight is 2000~3000.；
(2) preparation without styrene UPR with low shrinkage resin：
A, prepare raw material, according to the mass fraction, including 60~75 parts of unsaturated polyester (UP) oligomer, 0.02~0.05 part of polymerization inhibitor,
0~0.5 part of 25~40 parts of diluent, 0.2-2 parts of initiator and accelerator；
When reaction solution obtained by b, step (1) is cooled to 120~140 DEG C, polymerization inhibitor is added, when continuing cool to 70~95 DEG C, plus
Enter diluent, be mixed evenly；
C, into mixed liquor obtained by step b initiator and accelerator are continuously added, after stirring, carried out freely at 70~90 DEG C
Base polymerisation, is made described without styrene UPR with low shrinkage resin.
3. the preparation method as claimed in claim 2 without styrene UPR with low shrinkage resin, it is characterized in that：Step
(1) saturated dicarboxylic acid/acid anhydride described in be phthalic acid, M-phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid,
Tetrabydrophthalic anhydride, HHPA, inner methylidyne tetrahydric phthalic anhydride, carbic anhydride, chlordene ENB two
One kind in formic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, malonic acid, adipic acid or decanedioic acid；
Unsaturated dicarboxylic acid/the acid anhydride is maleic anhydride, maleic acid, fumaric acid, itaconic acid or itaconic acid
One kind in acid anhydride；
The saturation dihydric alcohol ethylene glycol, diethylene glycol (DEG), triethylene glycol, propane diols, dipropylene glycol, tripropylene glycol, fourth two
One kind in alcohol, neopentyl glycol, hexylene glycol, cyclohexanediol or hydrogenated bisphenol A.
4. the preparation method as claimed in claim 2 without styrene UPR with low shrinkage resin, it is characterized in that：Step
(2) polymerization inhibitor is one in hydroquinones HQ, adjacent methyl hydroquinone OMHQ, benzoquinones BQ or TBHQ TBHQ in
Kind.
5. the preparation method as claimed in claim 2 without styrene UPR with low shrinkage resin, it is characterized in that：Step
(2) diluent described in is the acrylate of alicyclic structure, and its skeleton symbol is as follows：
6. the preparation method as claimed in claim 5 without styrene UPR with low shrinkage resin, it is characterized in that：It is described dilute
Releasing agent is specially
In one kind.
7. the preparation method as claimed in claim 2 without styrene UPR with low shrinkage resin, it is characterized in that：Step
(2) initiator described in be organic peroxide compound system, including two or more initiator composition initiation consolidate
Change system.
8. the preparation method as claimed in claim 7 without styrene UPR with low shrinkage resin, it is characterized in that：It is described to draw
Hair agent is specially benzoyl peroxide/dilauroyl peroxide BPO/LPO combinations, benzoyl peroxide/methyl ethyl ketone peroxide/mistake
Aoxidize t-butyl perbenzoate BPO/MEKP/TBPB combinations, cyclohexanone peroxide/di-tert-butyl peroxide CYHPO/DTBP combinations
Or one kind in double (2,4 dichloro benzene formyl) BPO/DCBP combinations of benzoyl peroxide/peroxidating.
9. the preparation method as claimed in claim 2 without styrene UPR with low shrinkage resin, it is characterized in that：Step
(2) accelerator described in is cobalt naphthenate or cobalt iso-octoate.
10. the application without styrene UPR with low shrinkage resin described in claim 1, it is characterized in that：It is applied to
In compression molding or pultrusion molding process.
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| CN201710418158.4A CN107141420B (en) | 2017-06-06 | 2017-06-06 | Without styrene UPR with low shrinkage resin and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663264A (en) * | 2017-09-21 | 2018-02-06 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin without styrene and preparation method and application |
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| CN113061212A (en) * | 2021-03-06 | 2021-07-02 | 江苏澳盛复合材料科技有限公司 | Unsaturated polyester resin composition and composite material prepared from same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107663264A (en) * | 2017-09-21 | 2018-02-06 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin without styrene and preparation method and application |
| CN107663264B (en) * | 2017-09-21 | 2019-09-10 | 广东溢达纺织有限公司 | A kind of unsaturated polyester resin and the preparation method and application thereof without styrene |
| CN109385061A (en) * | 2018-11-21 | 2019-02-26 | 浙江伟星实业发展股份有限公司 | A kind of resin button and preparation method thereof |
| CN113061212A (en) * | 2021-03-06 | 2021-07-02 | 江苏澳盛复合材料科技有限公司 | Unsaturated polyester resin composition and composite material prepared from same |
| CN113061212B (en) * | 2021-03-06 | 2022-06-21 | 江苏澳盛复合材料科技有限公司 | Unsaturated polyester resin composition and composite material prepared from same |
| CN114773536A (en) * | 2022-05-24 | 2022-07-22 | 新阳科技集团有限公司 | Preparation method of dicyclopentadiene type unsaturated polyester resin and preparation method of resin for insulating paint |
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