CN102977837A - Solventless double-component polyurethane adhesive and preparation method thereof - Google Patents
Solventless double-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN102977837A CN102977837A CN2012105191858A CN201210519185A CN102977837A CN 102977837 A CN102977837 A CN 102977837A CN 2012105191858 A CN2012105191858 A CN 2012105191858A CN 201210519185 A CN201210519185 A CN 201210519185A CN 102977837 A CN102977837 A CN 102977837A
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Abstract
The invention discloses a solventless double-component polyurethane adhesive and a preparation method thereof, belonging to the field of preparation of polyurethane adhesives. The adhesive is composed of a component A and a component B, wherein the component A is prepared by reacting nano silicon dioxide modified polyester polyol, polyisocyanate and polyether glycol; and the component B is prepared by mixing nano silicon dioxide modified polyester polyol and polyether glycol. By introducing nano silicon dioxide into the adhesive, the water absorptivity of the glue film formed after curing the solventless polyurethane adhesive can be obviously lowered, so that the glue film has high hydrolysis resistance, and furthermore, has high medium resistance; and the strength, toughness and heat resistance can be enhanced without lowering the transparency of the glue film, so that the adhesive has wider applicability in the field of composite flexible packaging, and has the advantages of no solvent residue and high safety.
Description
Technical field
The present invention relates to the polyurethane adhesive preparation field, especially relate to a kind of for field composite soft packaging anti-medium solvent free bi-component polyurethane adhesives of safety and environmental protection and preparation method thereof such as food, medicines.
Background technology
Along with people more and more pay attention to the hygienic safety performance of packing, the pressure from public opinion of the environment of preserving our planet grows with each passing day, and the solvent-free composite adhesive of environmental protection more and more receives people's concern.Composite soft packaging has outstanding food safety with the no-solvent type polyurethane adhesive, and the no-solvent type adhesive for polyurethane does not contain any solvent, so there is not the problem of dissolvent residual, can not pollute content, thereby have food safety.The solid content of no-solvent type adhesive for polyurethane is 100%, does not contain solvent, thereby in use, there is not solvent discharge, do not have three wastes material to produce yet, can be owing to the discharging of a large amount of solvents contaminate environment and affect the healthy of people, be the environmental type sizing agent.In addition, the compound flexible packing products of no-solvent type adhesive for polyurethane also has obvious economic advantages, and cost is low, energy consumption is low, steady quality, machine speed are fast.
At present, in some developed countries, most of low and middle-grade, large compound package material all uses solvent-free sizing agent to carry out laminating production.In China, solvent-free composite adhesive is also paid close attention to widely.Yet, in the solventless adhesive evolution, soft package structure some top grades, that particular requirement is arranged, and common solvent-free sizing agent does not also reach corresponding requirements at present.When being acid, alkali, the medium such as peppery, salty such as content, the composite soft packaging goods cause the low even delamination of stripping strength easily, affect the problems such as normal use of flexible package product.
Summary of the invention
The purpose of this invention is to provide a kind of anti-medium solvent free bi-component polyurethane adhesive and preparation method thereof, can significantly reduce the water-intake rate of no-solvent type polyurethane adhesive cured glue layer, thereby make glue-line have high anti-hydrolytic performance, and then has a high anti-dielectric behavior, anti-matter requirement in the time of can solving present common solvent-free sizing agent and can't satisfy content for acid, alkali, the medium such as peppery, salty causes the problem of the low even delamination of stripping strength easily.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive, it is characterized in that, this tackiness agent is comprised of A component and B component; Wherein,
Described A component is formed by nano-silicon dioxide modified polyester polyol, polyisocyanates and polyether glycol reaction;
Described B component is mixed by the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols.
Embodiment of the present invention also provides a kind of preparation method of solvent free bi-component polyurethane adhesive, and the method comprises:
Get nano-silicon dioxide modified polyester polyol, polyisocyanates and the polyether glycol of preparation A component by prescription of the present invention, and the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols of preparation B component:
Preparation A component: nano-silicon dioxide modified polyester polyol, polyether glycol are added reactor, 30～50 ℃ of lower mixing 1 hour, add polyisocyanates, 70～80 ℃ of lower reactions 3～4 hours, be down to normal temperature and namely get the A component;
Preparation B component: the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols is added reactor, 30～50 ℃ of lower mixing 1 hour, be down to normal temperature and namely get the B component;
A component and B set of dispense are combined into this solvent free bi-component polyurethane adhesive.
Can be found out by the above-mentioned technical scheme that provides, use A, B component to form tackiness agent in the embodiment of the present invention, and the A component is the affixture of the isocyanic ester of a kind of modification of being formed by nano-silicon dioxide modified polyester polyol, polyisocyanates and polyether glycol reaction, and the B component is the mixture of the polyvalent alcohol of a kind of modification of being mixed by the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols.Owing to all adopt nano-silicon dioxide modified polyester polyol in A component and B component, introducing by nano silicon, can significantly reduce the water-intake rate of no-solvent type polyurethane adhesive cured glue layer, thereby make glue-line have high anti-hydrolytic performance, and then have high anti-dielectric behavior.And because the introducing of nano silicon, also can improve intensity, toughness and the thermotolerance of glue-line, thereby when making this tackiness agent have the high resistance dielectric behavior, also has preferably anti-hydrolytic performance, and this tackiness agent does not have the pollution of solvent, and the wider scope of application can be arranged in the composite soft packaging field.
Embodiment
The below is clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills belong to protection scope of the present invention not making the every other embodiment that obtains under the creative work prerequisite.
The embodiment of the invention provides a kind of solvent free bi-component polyurethane adhesive, and this tackiness agent is comprised of A component and B component;
Wherein, the A component is formed by nano-silicon dioxide modified polyester polyol, polyisocyanates and polyether glycol reaction, is a kind of affixture of isocyanic ester of modification; The B component is mixed by the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols, is a kind of mixture of polyvalent alcohol of modification;
A component and B component can be by functional group's mol ratio :-NCO:-OH=1.2～this tackiness agent of 1.8:1.0 mix proportion.
In the above-mentioned tackiness agent, the nano-silicon dioxide modified polyester polyol in the A component accounts for 10～40% of A component gross weight, and the NCO% content of A component is 9%～21%, and the NCO% content of preferred A component is 11%～18%.
Nano-silicon dioxide modified polyester polyol in the B component accounts for 30～90% of B component gross weight, and polyether glycol accounts for 10～70% of B component gross weight.
Above-mentioned tackiness agent, in the nano-silicon dioxide modified polyester polyol in A component and the B component, the nanometer titanium dioxide silicone content is 5～30% of polyester polyol weight, be preferably 10～20%, the polyester polyol in the nano-silicon dioxide modified polyester polyol can adopt small molecules polyvalent alcohol and small molecules polyprotonic acid.This nano-silicon dioxide modified polyester polyol can be prepared by following methods, comprising:
In the small molecules polyvalent alcohol of polyester polyol, add nano silicon, ultrasonic wave (ultrasonic frequency be 20 ± 2KHz) and powerful dispersion machine (stirring velocity is 1200rpm) acting in conjunction under disperseed 1 hour, make the small molecules polyprotonic acid of described small molecules polyvalent alcohol and polyester polyol by functional group's mol ratio :-OH:-COOH=(1.2～1.6): 1 reaction namely makes nano-silicon dioxide modified polyester polyol.
The small molecules polyprotonic acid that polyester polyol in the nano-silicon dioxide modified polyester polyol in the above-mentioned A component adopts can be selected from: at least a in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, the Tetra hydro Phthalic anhydride;
The small molecules polyvalent alcohol that polyester polyol in the nano-silicon dioxide modified polyester polyol in the B component adopts can be selected from: ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, glycol ether, Triethylene glycol, tetraethylene-glycol, neopentyl glycol, 1, at least a in 6-hexylene glycol, cyclohexanedimethanol, glycerine, the TriMethylolPropane(TMP).
The small molecules polyprotonic acid that polyester polyol in the nano-silicon dioxide modified polyester polyol in A component and the B component adopts can be selected from: at least a in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, the Tetra hydro Phthalic anhydride.
Polyisocyanates in the above-mentioned tackiness agent A component is selected from:
Ditan-4,4 '-vulcabond (MDI), ditan-4,4 '-vulcabond and ditan-2, the mixture of 4 '-vulcabond (blending MDI, wherein 2,4 ' isomer part by weight 〉=25%), at least a in polyether-modified MDI (U-MDI), charing diimine modification MDI (C-MDI), poly methylene poly phenyl poly isocyanate (polymeric MDI claims again PAPI), the isophorone diisocyanate (IPDI).
Polyether glycol in the above-mentioned tackiness agent A component is selected from:
Molecular-weight average is that 400～2000 polyoxypropyleneglycol, molecular-weight average are at least a in 1000～2000 the polytetrahydrofuran diol.
The consumption of the polyether glycol in the above-mentioned tackiness agent B component be account for B component gross weight 10～50% the time, it is 400～2000 polyoxytrimethylene triol that polyether glycol can adopt separately molecular-weight average.
The consumption of the polyether glycol in the above-mentioned tackiness agent B component be account for B component gross weight 10～70% the time, polyether glycol can adopt with lower arbitrary group:
(1) polyether glycol is that 400～2000 polyoxytrimethylene triol, molecular-weight average are that 400～2000 polyoxypropyleneglycol and molecular-weight average are that 1000～2000 polytetrahydrofuran diol forms by molecular-weight average, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in the B component is 8～50%, molecular-weight average is that the weight ratio that 400～2000 polyoxypropyleneglycol accounts for the B component is 1～10%, and molecular-weight average is that the weight ratio that 1000～2000 polytetrahydrofuran diol accounts for the B component is 1～10%;
(2) polyether glycol is that 400～2000 polyoxytrimethylene triol and molecular-weight average are that 400～2000 polyoxypropyleneglycol forms by molecular-weight average, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in the B component is 9～50%, and molecular-weight average is that the weight ratio that 400～2000 polyoxypropyleneglycol accounts for the B component is 1～20%;
(3) polyether glycol is that 400～2000 polyoxytrimethylene triol and molecular-weight average are that 1000～2000 polytetrahydrofuran diol forms by molecular-weight average, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in the B component is 9～50%, and molecular-weight average is that the weight ratio that 1000～2000 polytetrahydrofuran diol accounts for the B component is 1～20%.
The embodiment of the invention also provides a kind of preparation method of solvent free bi-component polyurethane adhesive, and the method may further comprise the steps:
Get nano-silicon dioxide modified polyester polyol, polyisocyanates and the polyether glycol of preparation A component by above-mentioned prescription, and the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols of preparation B component:
Preparation A component: nano-silicon dioxide modified polyester polyol, polyether glycol are added reactor, 30～50 ℃ of lower mixing 1 hour, add polyisocyanates, 70～80 ℃ of lower reactions 3～4 hours, being down to normal temperature and namely getting the A component, is a kind of affixture of isocyanic ester of modification;
Preparation B component: the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols being added reactor, 30～50 ℃ of lower mixing 1 hour, be down to normal temperature and namely get the B component, is a kind of mixture of polyvalent alcohol of modification;
A component and B set of dispense are combined into this solvent free bi-component polyurethane adhesive, and A component and B component can be by functional group's mol ratio :-NCO:-OH=1.2～this tackiness agent of 1.8:1.0 mix proportion.
The embodiment of the invention is by all adopting nano-silicon dioxide modified polyester polyol in A, B component, introduce nano silicon, make a kind of inorganic/solvent free bi-component polyurethane adhesive of organic hybrid, the introducing of nano silicon, can significantly reduce the water-intake rate of no-solvent type polyurethane adhesive cured glue layer, thereby make glue-line have high anti-hydrolytic performance, and then have high anti-dielectric behavior; The introducing of nano silicon also can improve intensity, toughness, the thermotolerance of glue-line, does not reduce again the transparency of glue-line simultaneously.This adhesive for polyurethane has outstanding anti-hydrolytic performance and high resistance dielectric behavior, the flexible package product that can be widely used in content condition harshness, be the high-grade packing articles of acid, alkali, the medium such as peppery, salty such as content, thereby in the composite soft packaging field wider Application Areas arranged.
For ease of understanding, below in conjunction with specific embodiment implementation process of the present invention is described further.
Embodiment one
The embodiment of the invention provides a kind of solvent free bi-component polyurethane adhesive, this tackiness agent is comprised of A, B component, wherein, the A component is formed by nano-silicon dioxide modified polyester polyol, polyisocyanates and polyether glycol reaction, is a kind of affixture of isocyanic ester of modification; The B component is mixed by the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols, is a kind of mixture of polyvalent alcohol of modification;
A component and B component can be by functional group's mol ratio: this tackiness agent of-NCO:-OH=1.6:1.0 mix proportion.
The preparation method of this tackiness agent may further comprise the steps:
One, preparation A component:
(1) can prepare first nano-silicon dioxide modified polyester polyol, comprise:
(1) raw material: 1mol glycol ether, 0.3mol1,6-hexylene glycol, 0.8mol hexanodioic acid, 0.2mol m-phthalic acid, 38g nanometer grade silica;
(2) preparation process:
All small molecules polyvalent alcohols in will filling a prescription (being 1mol glycol ether and 0.3mol1, the 6-hexylene glycol) mix, and form the small molecules polyol blends;
The 38g nanometer grade silica is joined in the above-mentioned small molecules polyol blends, and form nano-silicon dioxide modified small molecules polyvalent alcohol powerful the dispersion 1 hour under ultrasonic wave and powerful dispersion machine acting in conjunction;
Add 0.8mol hexanodioic acid and 0.2mol m-phthalic acid in the pet reaction still, add above-mentioned nano-silicon dioxide modified small molecules polyvalent alcohol again, fasten feeding cover, heat temperature raising starts stirring after the material melting, passes into nitrogen; Temperature in the kettle reaches about 130 ℃ and begins water outlet, and 100～102 ℃ of control fractionation tower temperatures continue the reacting by heating still, and temperature in the kettle reaches about 230 ℃ and gone out theoretical water.Insulation 2h stopped to pass into nitrogen after water outlet was finished;
The sampling and testing acid number, the control acid number is below 25; Insulation is 220-230 ℃ in the still, and beginning progressively vacuumizes, and test hydroxyl value and acid number, and hydroxyl value reaches 112 ± 6, and acid number 0.3-1 is qualified; The cooling blowing makes nano-silicon dioxide modified polyester polyol, its hydroxyl value 113.6, acid number 0.9.
(2) synthetic A component:
(1) get the raw materials ready: 20 parts of above-mentioned nano-silicon dioxide modified polyester polyols, 20 parts of molecular-weight average are 1000 polyoxypropyleneglycol, and 5 parts of molecular-weight average are 1000 polytetrahydrofuran diol, 55 parts of MDI;
(2) preparation process:
With 20 parts of nano-silicon dioxide modified polyester polyols, 20 parts of molecular-weight average are 1000 polyoxypropyleneglycol, 5 parts of molecular-weight average are that 1000 polytetrahydrofuran diol adds in the reactor, 30 ℃ of lower mixing 1 hour, add 55 parts of MDI, 80 ℃ of lower reactions 4 hours, be down to normal temperature and namely get the A component.Test A component NCO%=14.68%.
Two, preparation B component:
(1) can prepare first nano-silicon dioxide modified polyester polyol, comprise:
(1) gets the raw materials ready: 1mol Triethylene glycol, 0.3mol1,2-propylene glycol, 0.2mol glycerine, 0.85mol hexanodioic acid, 0.38mol sebacic acid, 45g nanometer grade silica;
(2) preparation process: the preparation method can prepare with reference to this embodiment the step of the nano-silicon dioxide modified polyester polyol of preparation in the A component, makes nano-silicon dioxide modified polyester polyol, its hydroxyl value 116.1, acid number 1.0;
(2) synthetic B component:
(1) get the raw materials ready: 5 parts of molecular-weight average are 400 polyoxypropyleneglycol, and 20 parts of molecular-weight average are 400 polyoxytrimethylene triol, the nano-silicon dioxide modified polyester polyols of 75 parts of above-mentioned 2.1.2 preparations;
(2) synthetic B component: be 400 polyoxypropyleneglycol with 5 parts of molecular-weight average, 20 parts of molecular-weight average are 400 polyoxytrimethylene triol, and 75 parts of nano-silicon dioxide modified polyester polyols join in the reactor, 50 ℃ of lower mixing 1 hour, be down to normal temperature and namely get the B component;
Three, A component and B component cooperate by functional group's mol ratio-NCO:-OH=1.6:1.0, and multiple film forms this tackiness agent.With multiple film formed this tackiness agent printing PET/AL/COEX, 40 degree slaking 48h test heat-resisting water stability and anti-fruit juice stability, test result is as follows: before dress hot water and the hot fruit juice, stripping strength is 4.6N/15mm, and hot filling hot water is behind 48h, and stripping strength is 4.2～4.6N/15mm; Hot filling fruit juice is behind 48h, and stripping strength is 3.9～4.3N/15mm.
Embodiment two
The embodiment of the invention provides a kind of solvent free bi-component polyurethane adhesive, this tackiness agent is comprised of A, B component, wherein, the A component is formed by nano-silicon dioxide modified polyester polyol, polyisocyanates and polyether glycol reaction, is a kind of affixture of isocyanic ester of modification; The B component is mixed by the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols, is a kind of mixture of polyvalent alcohol of modification;
A component and B component can be by functional group's mol ratio: this tackiness agent of-NCO:-OH=1.55:1.0 mix proportion.
The preparation method of this tackiness agent may further comprise the steps:
One, preparation A component:
(1) prepare first nano-silicon dioxide modified polyester polyol, comprising:
(1) gets the raw materials ready: 0.8mol glycol ether, 0.2mol ethylene glycol, 0.4mol neopentyl glycol, 0.6mol hexanodioic acid, 0.2mol terephthalic acid, 0.2mol sebacic acid, 35g nanometer grade silica;
(2) preparation process: can be with reference to the step of the nano-silicon dioxide modified polyester polyol of preparation in the preparation A component among the embodiment one;
Make nano-silicon dioxide modified polyester polyol, hydroxyl value 141.3, acid number 0.8;
(2) synthetic A component:
(1) get the raw materials ready: 15 parts of above-mentioned nano-silicon dioxide modified polyester polyols, 15 parts of molecular-weight average are 2000 polyoxypropyleneglycol, and 17 parts of molecular-weight average are 400 polyoxypropyleneglycol, 23 parts of MDI, 25 parts of blending MDI, 5 parts of PAPI;
(2) preparation process:
Be that 2000 polyoxypropyleneglycol, 17 parts of molecular-weight average are that 400 polyoxypropyleneglycol adds in the reactor with 15 parts of above-mentioned nano-silicon dioxide modified polyester polyols, 15 parts of molecular-weight average, 30 ℃ of lower mixing 1 hour, add 23 parts of MDI, 25 parts of blending MDI, 5 parts of PAPI, 80 ℃ of lower reactions 4 hours, be down to normal temperature and namely get the A component.Test A component NCO%.
Two, preparation B component:
(1) prepare first nano-silicon dioxide modified polyester polyol, comprising:
(1) material preparation step: 0.58mol tetraethylene-glycol, 0.3mol cyclohexanedimethanol, 0.1mol1,4-butyleneglycol, 0.3mol glycerine, 0.55mol hexanodioic acid, 0.35mol sebacic acid, 0.2mol Tetra hydro Phthalic anhydride, 45g nanometer grade silica;
(2) preparation process: can with reference to the step of the nano-silicon dioxide modified polyester polyol of preparation in the preparation A component among the embodiment one, make nano-silicon dioxide modified polyester polyol, the test hydroxyl value;
(2) synthetic B component:
(1) get the raw materials ready: 30 parts of molecular-weight average are 700 polyoxytrimethylene triol, the nano-silicon dioxide modified polyester polyol of 70 parts of above-mentioned steps (2) preparation;
(2) synthetic B component: be 700 polyoxytrimethylene triol, the nano-silicon dioxide modified polyester polyols of 70 parts of above-mentioned 2.1.2 preparations with 30 parts of molecular-weight average, join in the reactor, 50 ℃ of lower mixing 1 hour, be down to normal temperature and namely get the B component;
Three, A component and B component cooperate by functional group's mol ratio-NCO:-OH=1.5:1.0, multiple film.Composite structure printing PET/AL/COEX, 40 degree slaking 48h test heat-resisting water stability and anti-fruit juice stability, test result is as follows: before dress hot water and the hot fruit juice, stripping strength is 4.8N/15mm, and hot filling hot water is behind 48h, and stripping strength is 4.4-4.7N/15mm; Hot filling fruit juice is behind 48h, and stripping strength is 4.1-4.4N/15mm.
Embodiment three
The embodiment of the invention provides a kind of solvent free bi-component polyurethane adhesive, this tackiness agent is comprised of A, B component, wherein, the A component is formed by nano-silicon dioxide modified polyester polyol, polyisocyanates and polyether glycol reaction, is a kind of affixture of isocyanic ester of modification; The B component is mixed by the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols, is a kind of mixture of polyvalent alcohol of modification;
A component and B component can be by functional group's mol ratio: this tackiness agent of-NCO:-OH=1.6:1.0 mix proportion.
One, preparation A component:
(1) prepare nano-silicon dioxide modified polyester polyol, comprising:
(1) gets the raw materials ready: 0.8mol glycol ether, 0.2mol1,6-hexylene glycol, 0.4mol neopentyl glycol, 0.6mol hexanodioic acid, 0.4mol sebacic acid, 40g nanometer grade silica;
(2) preparation process: can with reference to the step of the nano-silicon dioxide modified polyester polyol of preparation in the preparation A component among the embodiment one, make nano-silicon dioxide modified polyester polyol, the test hydroxyl value;
(2) synthetic A component:
(1) get the raw materials ready: 30 parts of above-mentioned nano-silicon dioxide modified polyester polyols, 13 parts of molecular-weight average are 1000 polyoxypropyleneglycol, and 9 parts of molecular-weight average are 1000 polytetrahydrofuran diol, 20 parts of CMDI, 25 parts of blending MDI, 3 parts of IPDI.
(2) preparation process:
Be that 1000 polyoxypropyleneglycol, 9 parts of molecular-weight average are that 1000 polytetrahydrofuran diol adds in the reactor with 30 parts of above-mentioned nano-silicon dioxide modified polyester polyols, 13 parts of molecular-weight average, 40 ℃ of lower mixing 1 hour, add 20 parts of C-MDI, 25 parts of blending MDI, 3 parts of IPDI, 80 ℃ of lower reactions 4 hours, be down to normal temperature and namely get the A component.Test A component NCO%.
Two, preparation B component:
(1) prepare nano-silicon dioxide modified polyester polyol, comprising:
(1) gets the raw materials ready: 0.68mol tetraethylene-glycol, 0.3mol1,6-hexylene glycol, 0.3mol glycerine, 0.55mol hexanodioic acid, 0.35mol sebacic acid, 0.2mol m-phthalic acid, 40g nanometer grade silica;
(2) preparation process: can with reference to the step of the nano-silicon dioxide modified polyester polyol of preparation in the preparation A component among the embodiment one, make nano-silicon dioxide modified polyester polyol, the test hydroxyl value;
(2) synthetic B component:
(1) get the raw materials ready: 25 parts of molecular-weight average are 1000 polyoxytrimethylene triol, the nano-silicon dioxide modified polyester polyol of 75 parts of above-mentioned steps (2) preparation;
(2) synthetic B component: be 1000 polyoxytrimethylene triol, the nano-silicon dioxide modified polyester polyols of 75 parts of above-mentioned 2.1.2 preparations with 25 parts of molecular-weight average, join in the reactor, 50 ℃ of lower mixing 1 hour, be down to normal temperature and namely get the B component.
Three, A component and B component cooperate by functional group's mol ratio-NCO:-OH=1.8:1.0, multiple film.Composite structure printing PET/AL/COEX, 40 degree slaking 48h test heat-resisting water stability and anti-fruit juice stability, test result is as follows: before dress hot water and the hot fruit juice, stripping strength is 5.6N/15mm, and hot filling hot water is behind 48h, and stripping strength is 5.1-5.4N/15mm; Hot filling fruit juice is behind 48h, and stripping strength is 4.6-5.0N/15mm.
The above; only for the better embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (10)
1. a solvent free bi-component polyurethane adhesive is characterized in that, this tackiness agent is comprised of A component and B component; Wherein,
Described A component is formed by nano-silicon dioxide modified polyester polyol, polyisocyanates and polyether glycol reaction;
Described B component is mixed by the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols.
2. tackiness agent according to claim 1 is characterized in that,
Nano-silicon dioxide modified polyester polyol in the described A component accounts for 10～40% of A component gross weight, and the NCO% content of A component is 9%～21%;
Nano-silicon dioxide modified polyester polyol in the described B component accounts for 30～90% of B component gross weight, and polyether glycol accounts for 10～70% of B component gross weight.
3. tackiness agent according to claim 1 and 2, it is characterized in that, in the nano-silicon dioxide modified polyester polyol in described A component and the B component, the nanometer titanium dioxide silicone content is 5～30% of polyester polyol weight, and described polyester polyol adopts small molecules polyvalent alcohol and small molecules polyprotonic acid.
4. tackiness agent according to claim 3 is characterized in that, described nano-silicon dioxide modified polyester polyol is prepared by following methods, comprising:
In the small molecules polyvalent alcohol of polyester polyol, add nano silicon, be to disperse 1 hour under the ultrasonic wave of 20 ± 2KHz and the powerful dispersion machine acting in conjunction that stirring velocity is 1200rpm in ultrasonic frequency, make the small molecules polyprotonic acid of described small molecules polyvalent alcohol and polyester polyol by functional group's mol ratio :-OH:-COOH=1.2～1.6:1.0 reaction, namely make nano-silicon dioxide modified polyester polyol.
5. tackiness agent according to claim 4, it is characterized in that the small molecules polyprotonic acid that polyester polyol in the nano-silicon dioxide modified polyester polyol in the described A component adopts is selected from: at least a in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, the Tetra hydro Phthalic anhydride;
The small molecules polyvalent alcohol that polyester polyol in the nano-silicon dioxide modified polyester polyol in the described B component adopts is selected from: ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, glycol ether, Triethylene glycol, tetraethylene-glycol, neopentyl glycol, 1, at least a in 6-hexylene glycol, cyclohexanedimethanol, glycerine, the TriMethylolPropane(TMP).
The small molecules polyprotonic acid that polyester polyol in the nano-silicon dioxide modified polyester polyol in described A component and the B component adopts is selected from: at least a in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, the Tetra hydro Phthalic anhydride.
6. tackiness agent according to claim 1 and 2 is characterized in that, the polyisocyanates in the described A component is selected from:
Ditan-2, the ditan of 4 '-vulcabond part by weight 〉=25%-4,4 '-vulcabond and ditan-2, the mixture of 4 '-vulcabond, ditan-4, at least a in 4 '-vulcabond, polyether-modified MDI, charing diimine modification MDI, poly methylene poly phenyl poly isocyanate, the isophorone diisocyanate.
7. tackiness agent according to claim 1 and 2 is characterized in that,
Polyether glycol in the described A component is selected from: molecular-weight average is that 400～2000 polyoxypropyleneglycol, molecular-weight average are at least a in 1000～2000 the polytetrahydrofuran diol;
The consumption of the polyether glycol in the described B component be account for B component gross weight 10～50% the time, it is 400～2000 polyoxytrimethylene triol that polyether glycol adopts molecular-weight average.
8. tackiness agent according to claim 1 is characterized in that, the consumption of the polyether glycol in the described B component be account for B component gross weight 10～70% the time, polyether glycol adopts with lower arbitrary group:
(1) be that 400～2000 polyoxytrimethylene triol, molecular-weight average are that 400～2000 polyoxypropyleneglycol and molecular-weight average are that 1000～2000 polytetrahydrofuran diol forms by molecular-weight average, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in the B component is 8～50%, molecular-weight average is that the weight ratio that 400～2000 polyoxypropyleneglycol accounts for the B component is 1～10%, and molecular-weight average is that the weight ratio that 1000～2000 polytetrahydrofuran diol accounts for the B component is 1～10%;
(2) be that 400～2000 polyoxytrimethylene triol and molecular-weight average are that 400～2000 polyoxypropyleneglycol forms by molecular-weight average, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in the B component is 9～50%, and molecular-weight average is that the weight ratio that 400～2000 polyoxypropyleneglycol accounts for the B component is 1～20%;
(3) be that 400～2000 polyoxytrimethylene triol and molecular-weight average are that 1000～2000 polytetrahydrofuran diol forms by molecular-weight average, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in the B component is 9～50%, and molecular-weight average is that the weight ratio that 1000～2000 polytetrahydrofuran diol accounts for the B component is 1～20%.
9. the preparation method of a solvent free bi-component polyurethane adhesive is characterized in that, the method comprises:
Get nano-silicon dioxide modified polyester polyol, polyisocyanates and the polyether glycol of preparation A component by the prescription of claim 1, and the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols of preparation B component:
Preparation A component: nano-silicon dioxide modified polyester polyol, polyether glycol are added reactor, 30～50 ℃ of lower mixing 1 hour, add polyisocyanates, 70～80 ℃ of lower reactions 3～4 hours, be down to normal temperature and namely get the A component;
Preparation B component: the pure and mild polyether glycol of nano-silicon dioxide modified polyester polyols is added reactor, 30～50 ℃ of lower mixing 1 hour, be down to normal temperature and namely get the B component;
A component and B set of dispense are combined into this solvent free bi-component polyurethane adhesive.
10. method according to claim 9 is characterized in that,
Nano-silicon dioxide modified polyester polyol in the described A component accounts for 10～40% of A component gross weight, and the NCO% content of A component is 9%～21%;
Nano-silicon dioxide modified polyester polyol in the described B component accounts for 30～90% of B component gross weight, and polyether glycol accounts for 10～70% of B component gross weight;
In the nano-silicon dioxide modified polyester polyol in described A component and the B component, the nanometer titanium dioxide silicone content is 5～30% of polyester polyol weight, and described polyester polyol adopts small molecules polyvalent alcohol and small molecules polyprotonic acid;
Described nano-silicon dioxide modified polyester polyol is prepared by following methods, comprising:
In the small molecules polyvalent alcohol of polyester polyol, add nano silicon, it is powerful the dispersion 1 hour under the ultrasonic wave of 20 ± 2KHz and the powerful dispersion machine acting in conjunction that stirring velocity is 1200rpm in ultrasonic frequency, make the small molecules polyprotonic acid of described small molecules polyvalent alcohol and polyester polyol by functional group's mol ratio :-OH:-COOH=1.2～1.6:1 reaction, namely make nano-silicon dioxide modified polyester polyol.
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| CN110157371A (en) * | 2019-06-04 | 2019-08-23 | 无锡市万力粘合材料股份有限公司 | The preparation method of food flexible packing complex function adhesive |
| CN111395011A (en) * | 2020-05-21 | 2020-07-10 | 烟台同兴过滤科技有限公司 | Filter cloth gluing process |
| CN112301505A (en) * | 2020-10-16 | 2021-02-02 | 高梵(浙江)信息技术有限公司 | Seamless down-filled down jacket fabric and production method thereof |
| CN114316243A (en) * | 2021-12-29 | 2022-04-12 | 山东一诺威新材料有限公司 | Silicon dioxide modified polyether polyol and preparation method thereof |
| CN115536805A (en) * | 2022-09-27 | 2022-12-30 | 北京高盟新材料股份有限公司 | Solvent-free polyurethane composition and preparation method thereof |
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