CN102627938A - 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
A preparation method of an nonsaturated polyester polyurethane segmented copolymer solvent-free adhesive comprises the following steps of: gradually performing polycondensation by the use of dihydric alcohol, maleic anhydride and o phthalic anhydride to generate hydroxyl-terminated nonsaturated oligoester; gradually performing polyaddition by the use of nonsaturated oligopolymer, diisocyanate and polyethylene glycol with styrene being as a solvent to generate an isocyanate-terminated nonsaturated polyester polyurethane segmented prepolymer solution; blocking the prepolymer by methacrylic acid-beta hydroxyl ethyl to obtain alkene-terminated nonsaturated polyester polyurethane segmented active prepolymer base stock; and compounding the active prepolymer base stock and an auxiliary agent styrene solution to prepare the nonsaturated polyester polyurethane segmented 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 human 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 is meant that each component of tackiness agent all forms bonding coat and do not have volatilization 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 type of environmentally friendly tackiness agent.Adhesive for solvent-free use is before curing, for guaranteeing the 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; Mode through physics or chemistry between all components in the tackiness agent interacts and common forms the bonding coat matrix material, and does not have volatiles, for reaching this purpose; In the adhesive formula design, must take into full account the interaction between each component, from the instrumental analysis of binder ingredients; Have only as forming adhesion-layer materials through chemical action between the solvent of adjusting the adhesive flow sex change and the adhesive resin; Just can effectively reduce the discharging of organic solvent, just might realize zero VOC discharging, therefore; Adhesive for solvent-free use is in formulating of recipe, and 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, and low VOC tackiness agent gets into 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 of forming 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 big, attachment fastness is low, poor impact toughness.
Unsaturated polyester resin (UPR) is one of the thermosetting adhesive resin comparatively rapidly of development both at home and abroad in recent years.Yet UPR is hard and crisp after solidifying, and impact property is poor, high its widespread uses of shortcoming restriction such as (general cure shrinkage are 7%～8%) of cure shrinkage.At present, the modification to 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 considers, when synthetic UPR, introduces soft segment, can effectively improve fragility, but too much adding soft segment, can cause resin solidification after physical strength descend.Is a kind of faster method of modifying of development in recent years based on the second phase material elastomerics to the UPR toughening modifying.What elastic body toughening was commonly used is that fluid rubber is toughness reinforcing.Owing 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 to UPR mainly is to reduce its cure shrinkage through adding thermoplasticity shrinking agent (LPA).Shrinking agent commonly used has PS, polymethylmethacrylate and dially phthalate etc., has also developed polycaprolactone, modified polyurethane and FM butyl ester etc.Adopt the fragility of LPA modification can improvement UPR, reduce cure shrinkage, improve shock strength, but can reduce the tensile strength of UPR.
Urethane has high-flexibility as the extraordinary elastomerics of a kind of property reconciled, and both maximize favourable factors and minimize unfavourable ones by bound energy, and performance advantage has separately not only reduced cure shrinkage, has also increased toughness.All the time, people concentrate on through adding polyurethane elastomer and UPR physical blending reaching the purpose of modification to the modification of UPR, but often when improving its impelling strength, reduction cure shrinkage, have also reduced other mechanical property.
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: dibasic acid anhydride, terepthaloyl moietie, YLENE, the vitriol oil are added successively be equipped with in electronic stirring, water trap, TM, the electric mantle heated reaction vessel, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, and MALEIC ANHYDRIDE is a unsaturated acid anhydride; The mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, and hydroxyl molar excess percentage ratio is 20%～100%, and the oligopolymer number-average molecular weight is 500～2000; Start stirring after being heated to the solid dissolving, 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 divalent alcohol that measures, be evacuated to hydroxyl value and meet the requirements; Steam solvent, treat to add vinylbenzene when resin is cooled to below 50 ℃, stir; Stop stirring, filter discharging, keep in Dark Place;
The preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: earlier with step (1) synthetic terminal hydroxy group unsaturated polyester ester oligomer styrene solution, vulcabond and dibutyl tin laurate adding are equipped with in electronic stirring, condensing surface, TM, the electric mantle heated reaction vessel, are warming up to 60 ℃ of insulation reaction; System system-NCO%, i.e. NCO 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; Stop heating, qualified with reactive thinner adjustment viscosity, stop stirring; Filter discharging, keep in Dark Place;
The preparation of step (3) unsaturated polyester block polymers of polyurethane tackiness agent: accurately take by weighing base-material, filler and auxiliary agent by prescription, in container, mix, high-speed stirring is uniformly dispersed, and is tackiness agent first component with reactive thinner adjustment viscosity to qualified discharging; Curing catalyst is dissolved in the 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, glued construction each item performance index reach maximum bond strength.
The present invention adopts divalent alcohol, MALEIC ANHYDRIDE and phthalic anhydride to pass through progressively polycondensation and generates terminal hydroxy group unsaturated polyester ester oligomer; Unsaturated oligopolymer and vulcabond, polyoxyethylene glycol are the progressively unsaturated polyester polyurethane blocks prepolymer base-material of addition polymerization generation terminal isocyanate groups of solvent warp with vinylbenzene; 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, no Prevent Carbon Contamination, environmental friendliness, and is 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 reaction formula 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: dibasic acid anhydride, terepthaloyl moietie, YLENE, the vitriol oil are added successively be equipped with in electronic stirring, water trap, TM, the electric mantle heated reaction vessel, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, and MALEIC ANHYDRIDE is a unsaturated acid anhydride; The mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, and hydroxyl molar excess percentage ratio is 20%～100%, and the oligopolymer number-average molecular weight is 500～2000; Start stirring after being heated to the solid dissolving, 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 divalent alcohol that measures, be evacuated to hydroxyl value and meet the requirements; Steam solvent, treat to add vinylbenzene when resin is cooled to below 50 ℃, stir; Stop stirring, filter discharging, keep in Dark Place;
The preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: earlier with step (1) synthetic terminal hydroxy group unsaturated polyester ester oligomer styrene solution, vulcabond and dibutyl tin laurate adding are equipped with in electronic stirring, condensing surface, TM, the electric mantle heated reaction vessel, are warming up to 60 ℃ of insulation reaction; System system-NCO%, i.e. NCO 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; Stop heating, qualified with reactive thinner adjustment viscosity, stop stirring; Filter discharging, keep in Dark Place;
The preparation of step (3) unsaturated polyester block polymers of polyurethane tackiness agent: accurately take by weighing base-material, filler and auxiliary agent by prescription, in container, mix, high-speed stirring is uniformly dispersed, and is tackiness agent first component with reactive thinner adjustment viscosity to qualified discharging; Curing catalyst is dissolved in the 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, glued construction each item performance index reach maximum bond strength.
When the above (2) unsaturated polyester block polymers of polyurethane base-material of the above step prepared, hydroxy component was made up of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and the two 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 a tolylene diisocyanate, and NCO 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 methylacrylic 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 90%～95% and 4%～9% of tackiness agent first component formula total mass respectively.
When the above step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepares; Auxiliary agent comprises solidifying agent BPO, skimmer organic silicon acrylic ester, softening agent paraffin and stablizer para benzoquinone, and consumption accounts for 0.6%, 0.2%, 0.1% and 0.1% of tackiness agent first component formula total mass respectively.
When the above step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepared, curing catalyst was N, accelerine, and tackiness agent second component is N, the reactive thinner solution of accelerine, mass concentration is 10%.
When the above step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepared, reactive thinner was made up of TEB 3K and Bing Xisuandingzhi, and the two 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.
Further launch the present invention with more concrete embodiment below.
(1) terminal hydroxy group unsaturated polyester ester oligomer is synthetic
The MALEIC ANHYDRIDE that measures, phthalic anhydride, terepthaloyl moietie, YLENE, catalyzer added successively be equipped with in electronic stirring, water trap, TM, the electric mantle heated reaction vessel, start stirring after being heated to the solid dissolving, and be warming up to 150 ℃; Reacted 2 hours, and be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the divalent alcohol that measures; Being evacuated to hydroxyl value meets the requirements; Steam solvent, treat to add vinylbenzene when resin is cooled to below 50 ℃, stir; Discharging is subsequent use, keeps in Dark Place.
(2) the unsaturated polyester block polymers of polyurethane is synthetic
The first step synthetic unsaturated polyester resin (UPR) styrene solution and tolylene diisocyanate (TDI) that measures and the adding of catalyzer dibutyl tin laurate are equipped with in electronic stirring, water trap, TM, the electric mantle heated reaction vessel; Be warming up to 60 ℃ of insulation reaction; When-NCO%, when promptly NCO content tended towards stability, it is constant to system-NCO% that the adding polyglycol ether carries out chain extending reaction; Add methylacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock; Stopped reaction, discharging is subsequent use, keeps in Dark Place.
(3) preparation of unsaturated polyester block polymers of polyurethane adhesive for solvent-free use
Press table 1 prescription and prepare base-material, calcene filler and auxiliary agent, in container, mix, high-speed stirring is uniformly dispersed, and is tackiness agent first component with reactive thinner adjustment viscosity to qualified discharging; Curing catalyst N, accelerine are dissolved in the reactive thinner, and being formulated as 10% solution is the second component; First, second component is even by 10: 1 mixed, bonding sample preparation, and ambient cure 5 minutes detects glued construction each item performance index.
Table 1 unsaturated polyester block polymers of polyurethane adhesive for solvent-free use formula table
Claims (9)
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: dibasic acid anhydride, terepthaloyl moietie, YLENE, the vitriol oil are added successively be equipped with in electronic stirring, water trap, TM, the electric mantle heated reaction vessel, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, and MALEIC ANHYDRIDE is a unsaturated acid anhydride; The mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2～3: 1, and hydroxyl molar excess percentage ratio is 20%～100%, and the oligopolymer number-average molecular weight is 500～2000; Start stirring after being heated to the solid dissolving, 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 divalent alcohol that measures, be evacuated to hydroxyl value and meet the requirements; Steam solvent, treat to add vinylbenzene when resin is cooled to below 50 ℃, stir; Stop stirring, filter discharging, keep in Dark Place;
The preparation of step (2) unsaturated polyester block polymers of polyurethane base-material: earlier with step (1) synthetic terminal hydroxy group unsaturated polyester ester oligomer styrene solution, vulcabond and dibutyl tin laurate adding are equipped with in electronic stirring, condensing surface, TM, the electric mantle heated reaction vessel, are warming up to 60 ℃ of insulation reaction; System system-NCO%, i.e. NCO 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; Stop heating, qualified with reactive thinner adjustment viscosity, stop stirring; Filter discharging, keep in Dark Place;
The preparation of step (3) unsaturated polyester block polymers of polyurethane tackiness agent: accurately take by weighing base-material, filler and auxiliary agent by prescription, in container, mix, high-speed stirring is uniformly dispersed, and is tackiness agent first component with reactive thinner adjustment viscosity to qualified discharging; Curing catalyst is dissolved in the 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, glued construction each item performance index reach maximum bond strength.
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 made up of terminal hydroxy group unsaturated polyester ester oligomer and polyoxyethylene glycol, and the two mol ratio is 1: 2～1; The polymerization degree of polyglycol ether is 5～10.
3. according to the preparation method of the described unsaturated polyester block polymers of polyurethane of claim 1 adhesive for solvent-free use; It is characterized in that: when step (2) unsaturated polyester block polymers of polyurethane prepares; Vulcabond is a tolylene diisocyanate; NCO molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000.
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 (2) unsaturated polyester block polymers of polyurethane base-material prepares; End-capping reagent is methylacrylic acid-β hydroxyl ethyl ester, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
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 prepared, base-material and filler accounted for 90%～95% and 4%～9% of tackiness agent first component formula total mass respectively.
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: when step (3) unsaturated polyester block polymers of polyurethane adhesive for solvent-free use prepares; Auxiliary agent comprises solidifying agent BPO, skimmer organic silicon acrylic ester, softening agent paraffin and stablizer para benzoquinone, and consumption accounts for 0.6%, 0.2%, 0.1% and 0.1% of tackiness agent first component formula total mass respectively.
7. 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, and tackiness agent second component is N; The reactive thinner solution of accelerine, mass concentration are 10%.
8. 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 made up of TEB 3K and Bing Xisuandingzhi, and the two mass ratio is 2～1: 1.
9. 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 ratio of first, second component is 10: 1, and the curing environment temperature is not less than 20 ℃, and be 5 minutes set time.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2020199175A1 (en) * | 2019-04-04 | 2020-10-08 | Dow Global Technologies Llc | Solventless adhesive composition and method for preparing thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235129A (en) * | 2008-03-05 | 2008-08-06 | 安徽大学 | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2020199175A1 (en) * | 2019-04-04 | 2020-10-08 | Dow Global Technologies Llc | Solventless adhesive composition and method for preparing thereof |
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