CN102627938B - Preparation method of nonsaturated polyester polyurethane segmented copolymer solvent-free adhesive - Google Patents
Preparation method of nonsaturated polyester polyurethane segmented copolymer solvent-free adhesive Download PDFInfo
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Abstract
不饱和聚酯聚氨酯嵌段共聚物无溶剂粘合剂的制备方法，采用二元醇、顺丁烯二酸酐和苯酐通过逐步缩聚生成羟端基不饱和聚酯齐聚物；不饱和齐聚物与二异氰酸酯、聚乙二醇以苯乙烯为溶剂经逐步加聚生成异氰酸酯端基的不饱和聚酯聚氨酯嵌段预聚物溶液；预聚物以甲基丙烯酸-β羟乙酯封端得到烯端基不饱和聚酯聚氨酯嵌段活性预聚物基料；活性预聚物基料与苯乙烯溶液助剂复配制备不饱和聚酯聚氨酯嵌段共聚物无溶剂粘合剂。The preparation method of unsaturated polyester polyurethane block copolymer solvent-free adhesive adopts glycol, maleic anhydride and phthalic anhydride to generate hydroxyl-terminated unsaturated polyester oligomer through gradual polycondensation; unsaturated oligomer With diisocyanate and polyethylene glycol, the unsaturated polyester polyurethane block prepolymer solution of isocyanate end group is formed through gradual addition polymerization with styrene as solvent; the prepolymer is blocked with β-hydroxyethyl methacrylate to obtain olefin Terminal unsaturated polyester polyurethane block active prepolymer base material; active prepolymer base material and styrene solution additives are compounded to prepare unsaturated polyester polyurethane block copolymer solvent-free adhesive.
Description
Technical field
The present invention relates to a kind of preparation method of tackiness agent.
Background technology
Along with the enhancing of mankind's environmental consciousness and the enforcement of countries in the world environmental regulation, modern tackiness agent industry has formed the environmentally friendly mainstream development direction of Water-borne modification, high curing and solvent free.The solvent free of tackiness agent refers to that each component of tackiness agent all forms bonding coat and non-volatile loss after tackiness agent solidifies, and can realize the zero VOC discharging of tackiness agent, does not form the Prevent Carbon Contamination of environment, belongs to the main Types of environmentally friendly tackiness agent.adhesive for solvent-free use is before curing, for guaranteeing preparation and the workability of tackiness agent, from form, similar with Solvent Adhesive, belong to the polymer compound fluid, when difference is that adhesive for solvent-free use solidifies, interact and jointly form the bonding coat matrix material by physics or chemical mode between all components in tackiness agent, and non-volatile component, for reaching this purpose, in the adhesive formula design, must take into full account the interaction between each component, instrumental analysis from binder ingredients, only have as forming adhesion-layer materials by chemical action between the solvent of adjusting the adhesive flow sex change and adhesive resin, just can effectively reduce the discharging of organic solvent, just likely realize zero VOC discharging, therefore, adhesive for solvent-free use is in formulating of recipe, the reaction compatibility of seeking solvent and resin is the core of tackiness agent solvent free research.Unremitting effort through the tackiness agent scientific worker, obtaining certain progress aspect the tackiness agent solvent free, at present, the high solid tackiness agent has significantly reduced the organic solvent content of adhesive composition, low VOC tackiness agent enters the application stage, but such tackiness agent still can't be realized zero VOC discharging, and the research of adhesive for solvent-free use still needs long-term and unremitting effort; The adhesive for solvent-free use that forms with unsaturated polyester and unsaturated solvent (reactive thinner) is one of important kind of numerous adhesive for solvent-free use, but its widespread uses of restriction such as its cure shrinkage is large, attachment fastness is low, poor impact toughness.
Unsaturated polyester resin (UPR) is recent domestic development one of thermosetting adhesive resin comparatively rapidly.Yet UPR is hard and crisp after solidifying, and impact property is poor, and the shortcomings such as cure shrinkage high (general cure shrinkage is 7%～8%) restrict its widespread use.At present, the modification for UPR mainly concentrates on its toughening modifying and low two aspects of modification of shrinking., in order to improve the shock resistance of UPR goods, often need UPR to carry out the toughness modification.From introducing the macromole flexible chain, the mobility that increases crosslinked network chain is considered, introduces soft segment when synthetic UPR, can effectively improve fragility, but the too much soft segment that adds, can cause resin solidification after physical strength descend.Development in recent years a kind of method of modifying faster based on second-phase elastic properties of materials body to the UPR toughening modifying.What elastic body toughening was commonly used is that fluid rubber is toughness reinforcing.Due to the high-flexibility of rubber phase, significantly improved the toughness of UP, though rubber elastomer can increase substantially shock strength, stretching, flexural strength, resistance toheat descend to some extent.
At present, the low contraction modification for UPR is mainly to reduce its cure shrinkage by adding thermoplasticity shrinking agent (LPA).Shrinking agent commonly used has polystyrene, polymethylmethacrylate and dially phthalate etc., has also developed polycaprolactone, modified polyurethane and cellulose acetate butyl ester etc.Adopt the LPA modification can improve the fragility of UPR, reduce cure shrinkage, improve shock strength, but can reduce the tensile strength of UPR.
Urethane, as the extraordinary elastomerics of a kind of property reconciled, has high-flexibility, and both are in conjunction with maximizing favourable factors and minimizing unfavourable ones, and performance advantage separately, not only reduced cure shrinkage, also increased toughness.All the time, people concentrate on by adding polyurethane elastomer and UPR physical blending to reach the purpose of modification for the modification of UPR, but have often also reduced other mechanical property when improving its impelling strength, reducing cure shrinkage.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use.
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use, the steps include:
synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer: with dibasic acid anhydride, ethylene glycol, dimethylbenzene, the vitriol oil adds successively electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, hydroxyl molar excess percentage ratio is 20%～100%, the oligopolymer number-average molecular weight is 500～2000, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, stop stirring, filter discharging, keep in Dark Place,
the preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: the terminal hydroxy group unsaturated polyester ester oligomer styrene solution of first step (1) being synthesized, vulcabond and dibutyl tin laurate add electric stirring are housed, condenser, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, system-NCO% processed, it is the isocyanate group content constant, add polyglycol ether carry out block reaction to-NCO% is constant, add end-capping reagent carry out end capping to system-NCO% equals at 0 o'clock, stopped heating, adjust viscosity with reactive thinner qualified, stop stirring, filter discharging, keep in Dark Place,
The preparation of step (3) unsaturated polyester block polymers of polyurethane tackiness agent: by formula, accurately take base-material, filler and auxiliary agent, mix in container, high-speed stirring, be uniformly dispersed, and take reactive thinner, adjusts viscosity to qualified discharging as tackiness agent first component; Curing catalyst is dissolved in reactive thinner, and being formulated as 10% solution is the second component; First, second component mixes in proportion, bonding sample preparation, and ambient cure 5 minutes, the glued construction property indices reaches maximum bond strength.
The present invention adopts dibasic alcohol, MALEIC ANHYDRIDE and phthalic anhydride to generate terminal hydroxy group unsaturated polyester ester oligomer by Step Condensation; Unsaturated oligopolymer and vulcabond, polyoxyethylene glycol generate the unsaturated polyester polyurethane blocks prepolymer base-material of terminal isocyanate groups through addition polymerization progressively take vinylbenzene as solvent; Prepolymer obtains alkene end group unsaturated polyester polyurethane blocks active prepolymer base-material with the Hydroxyethyl acrylate end-blocking; Active prepolymer base-material and additive compound prepare unsaturated polyester block polymers of polyurethane adhesive for solvent-free use.This tackiness agent has zero VOC discharging, without Prevent Carbon Contamination, environmental friendliness, normal temperature solidified, cure shrinkage is low, bonding intensity is high, impelling strength is good.
Embodiment
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use, adopts chemical equation to describe, and the steps include:
Synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer;
The preparation of step (2) unsaturated polyester block polymers of polyurethane base-material;
The preparation of step (3) unsaturated polyester block polymers of polyurethane tackiness agent.
Adopt written language to launch the present invention, the steps include:
synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer: with dibasic acid anhydride, ethylene glycol, dimethylbenzene, the vitriol oil adds successively electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, hydroxyl molar excess percentage ratio is 20%～100%, the oligopolymer number-average molecular weight is 500～2000, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, stop stirring, filter discharging, keep in Dark Place,
the preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: the terminal hydroxy group unsaturated polyester ester oligomer styrene solution of first step (1) being synthesized, vulcabond and dibutyl tin laurate add electric stirring are housed, condenser, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, system-NCO% processed, it is the isocyanate group content constant, add polyglycol ether carry out block reaction to-NCO% is constant, add end-capping reagent carry out end capping to system-NCO% equals at 0 o'clock, stopped heating, adjust viscosity with reactive thinner qualified, stop stirring, filter discharging, keep in Dark Place,
The preparation of step (3) unsaturated polyester block polymers of polyurethane tackiness agent: by formula, accurately take base-material, filler and auxiliary agent, mix in container, high-speed stirring, be uniformly dispersed, and take reactive thinner, adjusts viscosity to qualified discharging as tackiness agent first component; Curing catalyst is dissolved in reactive thinner, and being formulated as 10% solution is the second component; First, second component mixes in proportion, bonding sample preparation, and ambient cure 5 minutes, the glued construction property indices reaches maximum bond strength.
When the above (2) unsaturated polyester block polymers of polyurethane base-material of the above step prepared, hydroxy component was comprised of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and both mol ratio is 1: 2～1; The polymerization degree of polyglycol ether is 5～10.
When the above step (2) unsaturated polyester block polymers of polyurethane prepared, vulcabond was tolylene diisocyanate, and isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000.
When the above step (2) unsaturated polyester block polymers of polyurethane base-material prepared, end-capping reagent was methacrylic acid-β hydroxyl ethyl ester, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
When the above step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepared, base-material and filler accounted for respectively 90%～95% and 4%～9% of tackiness agent first component formula total mass.
When the above step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepares, auxiliary agent comprises solidifying agent dibenzoyl peroxide, defoamer organic silicon acrylic ester, softening agent paraffin and stablizer para benzoquinone, and consumption accounts for respectively 0.6%, 0.2%, 0.1% and 0.1% of tackiness agent first component formula total mass.
When the above step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepared, curing catalyst was DMA, and tackiness agent second component is the reactive thinner solution of DMA, and mass concentration is 10%.
When the above step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepared, reactive thinner was comprised of methyl methacrylate and butyl acrylate, and both mass ratio is 2～1: 1.
The present invention adopts two component adhesive, and the construction quality ratio of first, second component is 10: 1, and the curing environment temperature is not less than 20 ℃, and be 5 minutes set time.
Below with embodiment more specifically, further launch the present invention.
(1) terminal hydroxy group unsaturated polyester ester oligomer is synthetic
MALEIC ANHYDRIDE, phthalic anhydride, ethylene glycol, dimethylbenzene, the catalyzer that measures added successively in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, discharging is standby, keeps in Dark Place.
(2) the unsaturated polyester block polymers of polyurethane is synthetic
Unsaturated polyester resin (UPR) styrene solution that the first step is synthetic and the tolylene diisocyanate (TDI) that measures and catalyzer dibutyl tin laurate add in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed, be warming up to 60 ℃ of insulation reaction, when-NCO%, be that isocyanate group content is while tending towards stability, add polyglycol ether to carry out chain extending reaction constant to system-NCO%, add methacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock, stopped reaction, discharging is standby, keeps in Dark Place.
(3) preparation of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use
Press table 1 formula and prepare base-material, calcene filler and auxiliary agent, mix in container, high-speed stirring, be uniformly dispersed, and take reactive thinner, adjusts viscosity to qualified discharging as tackiness agent first component; The curing catalyst DMA is dissolved in reactive thinner, and being formulated as 10% solution is the second component; First, second component mixes in the ratio of 10: 1, bonding sample preparation, and ambient cure 5 minutes, detect the glued construction property indices.
Table 1 unsaturated polyester block polymers of polyurethane adhesive for solvent-free use formula table
Claims (6)
1. the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use, the steps include:
synthesizing of step (1) terminal hydroxy group unsaturated polyester ester oligomer: with dibasic acid anhydride, ethylene glycol, dimethylbenzene, the vitriol oil adds successively electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3:1, hydroxyl molar excess percentage ratio is 20%～100%, the oligopolymer number-average molecular weight is 500～2000, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, when being cooled to below 50 ℃, resin adds vinylbenzene, stir, stop stirring, filter discharging, keep in Dark Place,
the preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: the terminal hydroxy group unsaturated polyester ester oligomer styrene solution of first step (1) being synthesized, vulcabond and dibutyl tin laurate add electric stirring are housed, condenser, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, to system-NCO%, it is the isocyanate group content constant, add polyoxyethylene glycol carry out block reaction to-NCO% is constant, add end-capping reagent carry out end capping to system-NCO% equals at 0 o'clock, stopped heating, adjust viscosity with reactive thinner qualified, stop stirring, filter discharging, keep in Dark Place, wherein vulcabond is tolylene diisocyanate, isocyanate group molar excess percentage ratio is 50%～100%, the segmented copolymer number-average molecular weight is 2500～5000,
The preparation of step (3) unsaturated polyester block polymers of polyurethane tackiness agent: by formula, accurately take base-material, filler and auxiliary agent, mix in container, high-speed stirring, be uniformly dispersed, and take reactive thinner, adjusts viscosity to qualified discharging as tackiness agent first component; Curing catalyst is dissolved in reactive thinner, and being formulated as 10% solution is the second component; First, second component mixes in proportion, bonding sample preparation, and ambient cure 5 minutes, the glued construction property indices reaches maximum bond strength, and wherein base-material and filler account for respectively 90%～95% and 4%～9% of tackiness agent first component formula total mass; Auxiliary agent comprises solidifying agent dibenzoyl peroxide, defoamer organic silicon acrylic ester, softening agent paraffin and stablizer para benzoquinone, and consumption accounts for respectively 0.6%, 0.2%, 0.1% and 0.1% of tackiness agent first component formula total mass; Curing catalyst is DMA, and the construction quality of first, second component is than being 10:1.
2. the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use according to claim 1, it is characterized in that: when step (2) unsaturated polyester block polymers of polyurethane base-material prepares, hydroxy component is comprised of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and both mol ratio is 1:2～1; The polymerization degree of polyoxyethylene glycol is 5～10.
3. the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use according to claim 1, it is characterized in that: when step (2) unsaturated polyester block polymers of polyurethane base-material prepares, end-capping reagent is methacrylic acid-β hydroxyl ethyl ester, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
4. the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use according to claim 1, it is characterized in that: when step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepares, curing catalyst is N, accelerine, tackiness agent second component is N, the reactive thinner solution of accelerine, mass concentration are 10%.
5. the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use according to claim 1, it is characterized in that: when step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepares, reactive thinner is comprised of methyl methacrylate and butyl acrylate, and both mass ratio is 2～1:1.
6. the preparation method of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use according to claim 1, it is characterized in that adopting two component adhesive, the construction quality of first, second component is than being 10:1, and the curing environment temperature is normal temperature, and be 5 minutes set time.
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| CN105294976A (en) * | 2015-11-20 | 2016-02-03 | 嘉兴洛克化学工业有限公司 | Washing resistant polyurethane adhesive and preparation method thereof |
| CN106189993A (en) * | 2016-07-29 | 2016-12-07 | 无锡市万力粘合材料股份有限公司 | Steel plate overlay film monocomponent polyurethane glue hot-melt adhesive composition and preparation method thereof |
| CN113748182B (en) | 2019-04-04 | 2024-07-23 | 陶氏环球技术有限责任公司 | Solvent-free adhesive composition and method for preparing same |
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| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Preparation method of polybutadiene-based waterborne polyurethane and modified emulsion thereof |
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| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Preparation method of polybutadiene-based waterborne polyurethane and modified emulsion thereof |
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