CN103665311A - Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method - Google Patents
Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method Download PDFInfo
- Publication number
- CN103665311A CN103665311A CN201310371325.6A CN201310371325A CN103665311A CN 103665311 A CN103665311 A CN 103665311A CN 201310371325 A CN201310371325 A CN 201310371325A CN 103665311 A CN103665311 A CN 103665311A
- Authority
- CN
- China
- Prior art keywords
- unsaturated polyester
- dibasic alcohol
- flexible
- polyester resin
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Landscapes
- 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 relates to a modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method belonging to the field of high molecular polymerization. By synthesizing flexible unsaturated polyester dibasic alcohol through multi-step polymerization, the flexible group proportion and the hydroxyl value are controllable; a flexible unsaturated polyester dibasic alcohol, isocyanate and diluter blending method is easy to implement in the production process; the curing process is controllable, and room-temperature curing can be realized; and modified polyurethane/unsaturated polyester resin cured products are excellent in performance. The invention can be widely used in industrial, agricultural and transportation occasions as well as some occasions of special applications.
Description
Technical field:
The invention belongs to high molecular polymerization field, relate in particular to the flexible unsaturated polyester dibasic alcohol preparation method who utilizes a kind of modified polyurethane/unsaturated polyester resin.
Background technology:
Unsaturated polyester resin (UPR) has good over-all properties, and purposes is very extensive, is in thermosetting resin, to develop one of kind faster in recent years.But UPR exists the defect that fragility is larger, its range of application is restricted.The toughness that improves UPR becomes important problem.Adopt liquid rubber block to improve the fracture property of UPR, although this method has improved the toughness of UPR, its resistance toheat is had to detrimentally affect, and because viscosity improves the processing performance that has affected UPR.By molecular designing, the snappiness of adjusting molecular chain also can reach the object of toughness reinforcing UPR resin, but can affect its resistance toheat equally.It is the effective means that improves UPR toughness that urethane and UPR blend are prepared to inierpeneirating network structure material, and after modification, the mechanical property such as the flexural strength of UPR, shock strength obviously improves.
The general method that adopts polyurethane system to carry out modification to unsaturated polyester can be divided into following several substantially: 1, with urethane and the unsaturated polyester resin blend of active end group; 2, the segmented copolymer of preparing urethane and unsaturated polyester resin; 3, utilize isocyanic ester to carry out chain extension to unsaturated polyester; 4, form interpenetrating(polymer)networks urethane and unsaturated polyester resin mixtures.Above method is comparatively loaded down with trivial details, and product preparation cost is high, complicated operation, and has compatibility problem.By adding flexible macromole and keep unsaturated polyester resin end group in unsaturated polyester resin building-up process, be that the method for hydroxyl is simplified modified polyurethane/unsaturated polyester resin and operated, and the urethane/unsaturated polyester resin through modification keeps under the prerequisite of corresponding hardness, and tensile strength, shock strength and flexural strength are significantly improved.This kind of resin is with a wide range of applications in aerospace, automotive industry, shipbuilding and other industry.
Summary of the invention
The object of the invention is to utilize the preparation method of flexible unsaturated polyester dibasic alcohol modified polyurethane/unsaturated polyester resin.
A dibasic alcohol preparation method for modified polyurethane/unsaturated polyester resin, carries out according to following step:
(1) preparation of vibrin prepolymer:
First adopt dibasic alcohol, be warming up to 80 ℃; Add again monounsaturated dicarboxylic acid, in 1h, be warming up to 150 ℃, then be warming up to 210 ℃ with 10 ℃/h temperature rise rate; Logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, while being less than 20mgKOH/g to acid number, are cooled to 180 ℃;
(2) preparation of flexible unsaturated polyester dibasic alcohol:
Again add the flexible macromolecule dihydric alcohol of terminal hydroxy group, unsaturated dibasic acid, dibasic alcohol; With 10 ℃/h temperature rise rate, be warming up to 210 ℃, adopt the mode of polycondensation that flexible macromole and unsaturated polyester resin copolymerization are generated to segmented copolymer, while being less than 30mgKOH/g to acid number, to 180 ℃, vacuumize; Until acid number, be less than 10mgKOH/g when following, cooling down;
(3) urethane/unsaturated polyester resin of flexible unsaturated polyester dibasic alcohol modification solidifies:
Synthetic flexible unsaturated polyester dibasic alcohol is added to quantitative isocyanic ester, at 50 ℃ of low rate mixings, mix, finally add thinner; Finally prepare modified polyurethane/unsaturated polyester resin; Modified polyurethane/unsaturated polyester resin adds the catalyzer of resin quality consumption 0.01%-3.00%, the solidifying agent of resin quality consumption 0.1%-3.00%, and extremely suitable temperature pumps bubble and moisture, adds curing molding in mould.
Wherein the described dibasic alcohol of step (1) is the organic diol compounds such as ethylene glycol, propylene glycol, butyleneglycol, glycol ether, neopentyl glycol, dipropylene glycol; Monounsaturated dicarboxylic acid is phthalate anhydride, m-phthalic acid, terephthalic acid, tetrachlorophthalic tetrachlorophthalic anhydrid etc.; Dibasic alcohol and monounsaturated dicarboxylic acid mol ratio are 1-1.05:1.
Wherein the described flexible macromolecule dihydric alcohol of terminal hydroxy group of step (2) is hydroxy-terminated polybutadienes, terminal hydroxy group hydrogenated butadiene polymer, hydroxy-terminated polybutadienes-vinyl cyanide, liquid end hydroxy styrene-butadiene rubber, hydroxyl terminated polyisoprene, terminal hydroxy group hydrogenated polyisoprene etc., it is characterized by end group and be hydroxyl and middle segment alkene or the alkane that multiple segment is greater than 3 of attaching most importance to; Dibasic alcohol is the organic diol compounds such as ethylene glycol, propylene glycol, butyleneglycol, glycol ether, neopentyl glycol, dipropylene glycol; Unsaturated dibasic acid is the organic compound that contains two keys of two carboxyls such as MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE; The flexible macromolecule dihydric alcohol of terminal hydroxy group: the mol ratio of dibasic alcohol and unsaturated dibasic acid is 0.1-1:1-1.5:1.
Step (2) or add the flexible macromole diprotic acid of end carboxyl to replace the flexible macromolecule dihydric alcohol of terminal hydroxy group wherein, the flexible macromole diprotic acid of described end carboxyl is nbr carboxyl terminal, end carboxyl ethylene-propylene rubber(EPR) etc., it is characterized by end group and be carboxyl and middle segment alkene or the alkane that multiple segment is greater than 3 of attaching most importance to; Dibasic alcohol: the mol ratio of the flexible macromole diprotic acid of end carboxyl and unsaturated dibasic acid is 1.2-1.8:0.1-0.5:1.
Wherein the described isocyanic ester of step (3) be tolylene diisocyanate, diphenylmethanediisocyanate, isofoer diisocyanate, hexamethylene diisocyanate etc. with isocyanate functional group's organic compound, isocyanic ester and flexible unsaturated polyester dibasic alcohol mol ratio are 1-1.10:1; Thinner is vinylbenzene, the vinyl monomers such as methyl methacrylate, methyl acrylate, and thinner consumption is the 30%-60% of flexible unsaturated polyester dibasic alcohol quality consumption; Described catalyzer is that tertiary amine catalyst is as triethylenediamine, front three hydroxy-ethylenediamine, two (dimethylaminoethyl) ether etc.; Solidifying agent is organo-peroxide, as dibenzoyl peroxide, and the benzoyl peroxide tert-butyl ester etc., or be azo-compound Diisopropyl azodicarboxylate etc.; Or oxidation-reduction system, as dibenzoyl peroxide and DMA etc.
The described catalyzer of step (3) or be organo-metallic catalyst wherein, dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate etc.
The invention has the advantages that 1: adopt the flexible group ratio of the synthetic flexible unsaturated polyester dibasic alcohol of step-by-step polymerization and hydroxyl value controlled; 2: adopt the method for flexible unsaturated polyester dibasic alcohol, isocyanic ester and thinner blend, be easy to implement in process of production; 3: solidification process is controlled, can realize self-vulcanizing; 4: the curing rear excellent product performance of modified polyurethane/unsaturated polyester resin.The occasion that can be widely used in industry, agricultural, traffic and some special applications.
Embodiment
Below in conjunction with example, the present invention is described in further detail.
Embodiment 1
Polymerization procedure is as follows:
1, the preparation of vibrin prepolymer:
Add propylene glycol, be warming up to 80 ℃; Add again m-phthalic acid (dibasic alcohol and monounsaturated dicarboxylic acid mol ratio are 1-1.05:1).In 1h, be warming up to 150 ℃, then be warming up to 210 ℃ with 10 ℃/h temperature rise rate.Logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, while being less than 20mgKOH/g to acid number, are cooled to 180 ℃.
2, the preparation of flexible unsaturated polyester dibasic alcohol:
0.1 mole of the hydroxy-terminated polybutadienes that again adds molecular weight 1200,1.2 moles of glycol ethers, 1 mole of MALEIC ANHYDRIDE (the flexible macromolecule dihydric alcohol of terminal hydroxy group: the mol ratio of dibasic alcohol and unsaturated dibasic acid is 0.1:1.2:1).With 10 ℃/h temperature rise rate, be warming up to 210 ℃, adopt the mode of polycondensation that hydroxy-terminated polybutadienes and unsaturated polyester resin copolymerization are generated to segmented copolymer, while being less than 30mgKOH/g to acid number, to 180 ℃, vacuumize.Until acid number, be less than 10mgKOH/g when following, cooling down.
3, the urethane/unsaturated polyester resin of flexible unsaturated polyester dibasic alcohol modification solidifies:
1 mole of the 2 flexible unsaturated polyester dibasic alcohol synthesizing is added to 1.02 moles of toluene diisocyanate, at 50 ℃, drip and be uniformly mixed at a slow speed, finally add 50% flexible unsaturated polyester dibasic alcohol quality than thinner vinylbenzene.Finally prepare modified polyurethane/unsaturated polyester resin.Modified polyurethane/unsaturated polyester resin adds the triethylenediamine catalyzer of resin quality consumption 1.00%, the dibenzoyl peroxide solidifying agent of resin quality consumption 1.50%, pumps bubble and moisture after foaming, adds self-vulcanizing moulding in mould.
Embodiment 2
Polymerization procedure is as follows:
1, the preparation of vibrin prepolymer:
Add 1.03 moles of propylene glycol, be warming up to 80 ℃; Add again 1 mole of terephthalic acid (dibasic alcohol and monounsaturated dicarboxylic acid mol ratio are 1.03:1).In 1h, be warming up to 150 ℃, then be warming up to 210 ℃ with 10 ℃/h temperature rise rate.Logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, while being less than 20mgKOH/g to acid number, are cooled to 180 ℃.
2, the preparation of flexible unsaturated polyester dibasic alcohol:
0.2 mole of the liquid end hydroxy styrene-butadiene rubber that again adds molecular weight 2000,1.5 moles of glycol ethers, 1 mole of MALEIC ANHYDRIDE (the flexible macromolecule dihydric alcohol of terminal hydroxy group: the mol ratio of dibasic alcohol and unsaturated dibasic acid is 0.2:1.5:1).With 10 ℃/h temperature rise rate, be warming up to 210 ℃, adopt the mode of polycondensation that liquid end hydroxy styrene-butadiene rubber and unsaturated polyester resin copolymerization are generated to segmented copolymer, while being less than 30mgKOH/g to acid number, to 180 ℃, vacuumize.Until acid number, be less than 10mgKOH/g when following, cooling down.
3, the urethane/unsaturated polyester resin of flexible unsaturated polyester dibasic alcohol modification solidifies:
1 mole of the 2 flexible unsaturated polyester dibasic alcohol synthesizing is added to 1.05 moles of diphenylmethanediisocyanates, at 50 ℃, drip and be uniformly mixed at a slow speed, finally add 40% flexible unsaturated polyester dibasic alcohol quality than thinner vinylbenzene.Finally prepare modified polyurethane/unsaturated polyester resin.Modified polyurethane/unsaturated polyester resin adds the dibutyltin dilaurate catalyzer of resin quality consumption 1.00%, the dibenzoyl peroxide solidifying agent of resin quality consumption 1.50%, pumps bubble and moisture after foaming, adds 80 ℃ of curing moldings in mould.
Embodiment 3
Polymerization procedure is as follows:
1, the preparation of vibrin prepolymer:
Add 1.05 moles of butyleneglycols, be warming up to 80 ℃; Add again 1 mole of Tetra hydro Phthalic anhydride (dibasic alcohol and monounsaturated dicarboxylic acid mol ratio are 1.05:1).In 1h, be warming up to 150 ℃, then be warming up to 210 ℃ with 10 ℃/h temperature rise rate.Logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, while being less than 20mgKOH/g to acid number, are cooled to 180 ℃.
2, the preparation of flexible unsaturated polyester dibasic alcohol:
0.15 mole of the terminal hydroxy group hydrogenated butadiene polymer that again adds molecular weight 1500,1.4 moles of glycol ethers, 1 mole of MALEIC ANHYDRIDE (the flexible macromolecule dihydric alcohol of terminal hydroxy group: the mol ratio of dibasic alcohol and unsaturated dibasic acid is 0.15:1.4:1).With 10 ℃/h temperature rise rate, be warming up to 210 ℃, adopt the mode of polycondensation that terminal hydroxy group hydrogenated butadiene polymer and unsaturated polyester resin copolymerization are generated to segmented copolymer, while being less than 30mgKOH/g to acid number, to 180 ℃, vacuumize.Until acid number, be less than 10mgKOH/g when following, cooling down.
3, the urethane/unsaturated polyester resin of flexible unsaturated polyester dibasic alcohol modification solidifies:
1 mole of the 2 flexible unsaturated polyester dibasic alcohol synthesizing is added to 1.02 moles of toluene diisocyanate, at 50 ℃, drip and be uniformly mixed at a slow speed, finally add 40% flexible unsaturated polyester dibasic alcohol quality than thinner methyl methacrylate.Finally prepare modified polyurethane/unsaturated polyester resin.Modified polyurethane/unsaturated polyester resin adds the dibutyltin dilaurate catalyzer of resin quality consumption 1.00%, the dibenzoyl peroxide of resin quality consumption 1.50% and resin quality consumption 1%N, accelerine, after foaming, pump bubble and moisture, add self-vulcanizing moulding in mould.
Embodiment 4
Polymerization procedure is as follows:
1, the preparation of vibrin prepolymer:
Add 1.05 moles of propylene glycol, be warming up to 80 ℃; Add again 1 mole of Tetra hydro Phthalic anhydride (dibasic alcohol and monounsaturated dicarboxylic acid mol ratio are 1.05:1).In 1h, be warming up to 150 ℃, then be warming up to 210 ℃ with 10 ℃/h temperature rise rate.Logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, while being less than 20mgKOH/g to acid number, are cooled to 180 ℃.
2, the preparation of flexible unsaturated polyester dibasic alcohol:
Again add 1.4 moles of glycol ethers, 0.2 mole of the nbr carboxyl terminal of molecular weight 1500,1.0 moles of MALEIC ANHYDRIDE (dibasic alcohol: the mol ratio of the flexible macromole diprotic acid of end carboxyl and unsaturated dibasic acid is 1.4:0.2:1).With 10 ℃/h temperature rise rate, be warming up to 210 ℃, adopt the mode of polycondensation that nbr carboxyl terminal and unsaturated polyester resin copolymerization are generated to segmented copolymer, while being less than 30mgKOH/g to acid number, to 180 ℃, vacuumize.Until acid number, be less than 10mgKOH/g when following, cooling down.
3, the urethane/unsaturated polyester resin of flexible unsaturated polyester dibasic alcohol modification solidifies:
1 mole of the 2 flexible unsaturated polyester dibasic alcohol synthesizing is added to 1.02 moles of diphenylmethanediisocyanates, at 50 ℃, drip and be uniformly mixed at a slow speed, finally add 40% flexible unsaturated polyester dibasic alcohol quality than thinner vinylbenzene.Finally prepare modified polyurethane/unsaturated polyester resin.Modified polyurethane/unsaturated polyester resin adds the dibutyltin dilaurate catalyzer of resin quality consumption 1.00%, the dibenzoyl peroxide of resin quality consumption 1.00%, pumps bubble and moisture after foaming, adds 80 ℃ of curing moldings in mould.
Embodiment 5
Polymerization procedure is as follows:
1, the preparation of vibrin prepolymer:
Add 1.05 moles of propylene glycol, be warming up to 80 ℃; Add again 1 mole of terephthalic acid (dibasic alcohol and monounsaturated dicarboxylic acid mol ratio are 1.05:1).In 1h, be warming up to 150 ℃, then be warming up to 210 ℃ with 10 ℃/h temperature rise rate.Logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, while being less than 20mgKOH/g to acid number, are cooled to 180 ℃.
2, the preparation of flexible unsaturated polyester dibasic alcohol:
0.1 mole of the hydroxyl terminated polyisoprene that again adds molecular weight 2500,1.2 moles of glycol ethers, 1.0 moles of MALEIC ANHYDRIDE (the flexible macromolecule dihydric alcohol of terminal hydroxy group: the mol ratio of dibasic alcohol and unsaturated dibasic acid is 0.1:1.2:1.0).With 10 ℃/h temperature rise rate, be warming up to 210 ℃, adopt the mode of polycondensation that hydroxyl terminated polyisoprene and unsaturated polyester resin copolymerization are generated to segmented copolymer, while being less than 30mgKOH/g to acid number, to 180 ℃, vacuumize.Until acid number, be less than 10mgKOH/g when following, cooling down.
3, the urethane/unsaturated polyester resin of flexible unsaturated polyester dibasic alcohol modification solidifies:
1 mole of the 2 flexible unsaturated polyester dibasic alcohol synthesizing is added to 1.02 moles of diphenylmethanediisocyanates, at 50 ℃, drip and be uniformly mixed at a slow speed, finally add 40% flexible unsaturated polyester dibasic alcohol quality than thinner vinylbenzene.Finally prepare modified polyurethane/unsaturated polyester resin.Modified polyurethane/unsaturated polyester resin adds the dibutyltin dilaurate catalyzer of resin quality consumption 1.00%, the dibenzoyl peroxide of resin quality consumption 1.00%, pumps bubble and moisture after foaming, adds 80 ℃ of curing moldings in mould.
Urethane/unsaturated polyester resin partial properties after flexible unsaturated polyester dibasic alcohol modification prepared by example:
Above sample preparation and Mechanics Performance Testing are all made and test according to People's Republic of China's national standard method
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Those skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein are applied in other embodiment and needn't pass through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and the modification of making for the present invention all should be within protection scope of the present invention.
Claims (6)
1. a dibasic alcohol preparation method for modified polyurethane/unsaturated polyester resin, is characterized in that carrying out according to following step:
(1) preparation of vibrin prepolymer:
First adopt dibasic alcohol, be warming up to 80 ℃; Add again monounsaturated dicarboxylic acid, in 1h, be warming up to 150 ℃, then be warming up to 210 ℃ with 10 ℃/h temperature rise rate; Logical 180 ℃ of condensation polymerizations of nitrogen 3 hours, while being less than 20mgKOH/g to acid number, are cooled to 180 ℃;
(2) preparation of flexible unsaturated polyester dibasic alcohol:
Again add the flexible macromolecule dihydric alcohol of terminal hydroxy group, unsaturated dibasic acid, dibasic alcohol; With 10 ℃/h temperature rise rate, be warming up to 210 ℃, adopt the mode of polycondensation that flexible macromole and unsaturated polyester resin copolymerization are generated to segmented copolymer, while being less than 30mgKOH/g to acid number, to 180 ℃, vacuumize; Until acid number, be less than 10mgKOH/g when following, cooling down;
(3) urethane/unsaturated polyester resin of flexible unsaturated polyester dibasic alcohol modification solidifies:
Synthetic flexible unsaturated polyester dibasic alcohol is added to quantitative isocyanic ester, at 50 ℃ of low rate mixings, mix, finally add thinner; Finally prepare modified polyurethane/unsaturated polyester resin; Modified polyurethane/unsaturated polyester resin adds the catalyzer of resin quality consumption 0.01%-3.00%, the solidifying agent of resin quality consumption 0.1%-3.00%, and extremely suitable temperature pumps bubble and moisture, adds curing molding in mould.
2. the dibasic alcohol preparation method of a kind of modified polyurethane/unsaturated polyester resin according to claim 1, is characterized in that wherein the described dibasic alcohol of step (1) is ethylene glycol, propylene glycol, butyleneglycol, glycol ether, neopentyl glycol, dipropylene glycol; Monounsaturated dicarboxylic acid is phthalate anhydride, m-phthalic acid, terephthalic acid, tetrachlorophthalic tetrachlorophthalic anhydrid; Dibasic alcohol and monounsaturated dicarboxylic acid mol ratio are 1-1.05:1.
3. the dibasic alcohol preparation method of a kind of modified polyurethane/unsaturated polyester resin according to claim 1, is characterized in that wherein the described flexible macromolecule dihydric alcohol of terminal hydroxy group of step (2) is hydroxy-terminated polybutadienes, terminal hydroxy group hydrogenated butadiene polymer, hydroxy-terminated polybutadienes-vinyl cyanide, liquid end hydroxy styrene-butadiene rubber, hydroxyl terminated polyisoprene, terminal hydroxy group hydrogenated polyisoprene; Dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol, glycol ether, neopentyl glycol, dipropylene glycol; Unsaturated dibasic acid is the organic compound that contains two keys of two carboxyls such as MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE; The flexible macromolecule dihydric alcohol of terminal hydroxy group: the mol ratio of dibasic alcohol and unsaturated dibasic acid is 0.1-1:1-1.5:1.
4. the dibasic alcohol preparation method of a kind of modified polyurethane/unsaturated polyester resin according to claim 1, it is characterized in that wherein step (2) or add the flexible macromole diprotic acid of end carboxyl to replace the flexible macromolecule dihydric alcohol of terminal hydroxy group, the flexible macromole diprotic acid of described end carboxyl is nbr carboxyl terminal, end carboxyl ethylene-propylene rubber(EPR); Dibasic alcohol: the flexible macromole diprotic acid of end carboxyl: the mol ratio of unsaturated dibasic acid is 1.2-1.8:0.1-0.5:1.
5. the dibasic alcohol preparation method of a kind of modified polyurethane/unsaturated polyester resin according to claim 1, it is characterized in that wherein the described isocyanic ester of step (3) is tolylene diisocyanate, diphenylmethanediisocyanate, isofoer diisocyanate, hexamethylene diisocyanate, isocyanic ester and flexible unsaturated polyester dibasic alcohol mol ratio are 1-1.10:1; Thinner is vinylbenzene, methyl methacrylate, methyl acrylate, and thinner consumption is the 30%-60% of flexible unsaturated polyester dibasic alcohol quality consumption; Described catalyzer is that tertiary amine catalyst is as triethylenediamine, front three hydroxy-ethylenediamine, two (dimethylaminoethyl) ether; Solidifying agent is dibenzoyl peroxide, the benzoyl peroxide tert-butyl ester, Diisopropyl azodicarboxylate, dibenzoyl peroxide or DMA etc.; Or oxidation-reduction system, as dibenzoyl peroxide and DMA etc.
6. the dibasic alcohol preparation method of a kind of modified polyurethane/unsaturated polyester resin according to claim 1, is characterized in that the catalyzer that step (3) is wherein described or is dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310371325.6A CN103665311B (en) | 2013-08-22 | 2013-08-22 | A kind of dibasic alcohol preparation method of modified polyurethane/unsaturated polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310371325.6A CN103665311B (en) | 2013-08-22 | 2013-08-22 | A kind of dibasic alcohol preparation method of modified polyurethane/unsaturated polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103665311A true CN103665311A (en) | 2014-03-26 |
| CN103665311B CN103665311B (en) | 2016-04-13 |
Family
ID=50304162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310371325.6A Active CN103665311B (en) | 2013-08-22 | 2013-08-22 | A kind of dibasic alcohol preparation method of modified polyurethane/unsaturated polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103665311B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832139A (en) * | 2017-01-18 | 2017-06-13 | 新辉（中国）新材料有限公司 | Latex comprising polyurethane-modified Carboxy copolymer and preparation method thereof |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN107522854A (en) * | 2017-09-27 | 2017-12-29 | 浙江天和树脂有限公司 | A kind of preparation method of high flexibility unsaturated polyester resin |
| CN107573495A (en) * | 2017-09-20 | 2018-01-12 | 天守(福建)超纤科技股份有限公司 | A kind of flexible unsaturated polyester resin |
| CN107603202A (en) * | 2017-09-30 | 2018-01-19 | 南京晟强橡塑有限公司 | A kind of rubber pocket former polyurethane rubber bolster |
| CN108285524A (en) * | 2017-12-29 | 2018-07-17 | 浙江华峰新材料股份有限公司 | On-slip type polyurethane elastomer stoste and its preparation method and application |
| CN110724249A (en) * | 2019-10-11 | 2020-01-24 | 万华化学集团股份有限公司 | Polyester polyol, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195669A (en) * | 1997-04-08 | 1998-10-14 | 华东理工大学 | Rigidity plastics based on isocyanate and preparing method thereof |
| CN101613522A (en) * | 2009-07-14 | 2009-12-30 | 周志亮 | The high-strength resin based traffic guardrail structure composite material is resin dedicated |
| CN102212242A (en) * | 2011-04-14 | 2011-10-12 | 兰州理工大学 | Method for preparing unsaturated polyester polyurethane block copolymer composite material |
-
2013
- 2013-08-22 CN CN201310371325.6A patent/CN103665311B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195669A (en) * | 1997-04-08 | 1998-10-14 | 华东理工大学 | Rigidity plastics based on isocyanate and preparing method thereof |
| CN101613522A (en) * | 2009-07-14 | 2009-12-30 | 周志亮 | The high-strength resin based traffic guardrail structure composite material is resin dedicated |
| CN102212242A (en) * | 2011-04-14 | 2011-10-12 | 兰州理工大学 | Method for preparing unsaturated polyester polyurethane block copolymer composite material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832139A (en) * | 2017-01-18 | 2017-06-13 | 新辉（中国）新材料有限公司 | Latex comprising polyurethane-modified Carboxy copolymer and preparation method thereof |
| CN106832139B (en) * | 2017-01-18 | 2019-10-08 | 新辉（中国）新材料有限公司 | Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN107573495A (en) * | 2017-09-20 | 2018-01-12 | 天守(福建)超纤科技股份有限公司 | A kind of flexible unsaturated polyester resin |
| CN107522854A (en) * | 2017-09-27 | 2017-12-29 | 浙江天和树脂有限公司 | A kind of preparation method of high flexibility unsaturated polyester resin |
| CN107603202A (en) * | 2017-09-30 | 2018-01-19 | 南京晟强橡塑有限公司 | A kind of rubber pocket former polyurethane rubber bolster |
| CN108285524A (en) * | 2017-12-29 | 2018-07-17 | 浙江华峰新材料股份有限公司 | On-slip type polyurethane elastomer stoste and its preparation method and application |
| CN110724249A (en) * | 2019-10-11 | 2020-01-24 | 万华化学集团股份有限公司 | Polyester polyol, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103665311B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665311B (en) | A kind of dibasic alcohol preparation method of modified polyurethane/unsaturated polyester resin | |
| CN104448791B (en) | High-rigidity transparent polyurethane elastomer and preparation method thereof | |
| US11512164B2 (en) | Composite material comprising a polyurethane-polyacrylate resin matrix | |
| WO2017194034A1 (en) | Three-component low temperature-resistant polyester-type polyurethane elastomer and preparation method therefor | |
| CN100460437C (en) | Synthesis method of high-performance multipurpose urethane elastomer | |
| CN106634769B (en) | High-strength transparent adhesive and preparation method thereof | |
| CN107793989B (en) | Single-component polyurethane adhesive for plastic track and preparation method thereof | |
| CN102558496B (en) | Room temperature solidification polyurethane elastomer combination | |
| CN105482060A (en) | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof | |
| CN105153390B (en) | Environment-protecting polyurethane foaming tire combination material and preparation method thereof | |
| CN105968303B (en) | Preparation method of water-based epoxy resin curing agent | |
| CN113583198B (en) | Polyurethane acrylate composition and application thereof | |
| CN102504511B (en) | Polyurethane modified unsaturated polyester resin composition and preparation method thereof | |
| CN106674474A (en) | Polyurethane shoe material capable of demoulding quickly at room temperature, and preparation method of polyurethane shoe material | |
| CN102304214A (en) | Method for preparing micropore polyurethane vibration reduction buffering block for automobile | |
| CN106883591B (en) | Method for utilizing polyurethane waste material and elastomer | |
| CN110511390B (en) | Graphene end-crosslinked elastomer material and preparation method thereof | |
| CN102040824B (en) | Cast polyurethane elastomer composition for fashion model | |
| CN105254840A (en) | Polyurethane used for preparing load-bearing tire and preparing method thereof | |
| CN104356348A (en) | Hard hydrolysis-resistant, low-pitting performance and strong-peel strength polyurethane resin and preparation method thereof | |
| CN113755126B (en) | Adhesive and preparation method and application thereof | |
| CN112062937B (en) | Carbamate-based epoxy compounds, methods of making, and uses thereof | |
| CN106674480B (en) | Preparation method of NDI (Newcastle disease) -modified MDI (diphenylmethane diisocyanate) -based polyurethane microporous elastomer | |
| CN109251273B (en) | Method for synthesizing polyhydroxy polybutadiene through butadiene-hydroxyl-rubber graft modification | |
| CN102140245A (en) | Polyurethane elastomer composition for embedding LED (Light-Emitting Diode) lamp strip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211221 Address after: Room 407-2-6, building C, Tian'an Digital City, 588 Changwu South Road, Wujin high tech Industrial Development Zone, Changzhou City, Jiangsu Province 213000 Patentee after: CHANGZHOU XIAOGUO INFORMATION SERVICES Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |