CN102977837B - 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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- CN102977837B CN102977837B CN201210519185.8A CN201210519185A CN102977837B CN 102977837 B CN102977837 B CN 102977837B CN 201210519185 A CN201210519185 A CN 201210519185A CN 102977837 B CN102977837 B CN 102977837B
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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 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 no-solvent type polyurethane adhesive, and no-solvent type adhesive for polyurethane, containing 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%, not containing solvent, thereby in use, there is no solvent discharge, do not have three wastes material to produce yet, can be due to the discharge of a large amount of solvents contaminate environment and affect the healthy of people, be 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 solventless adhesive evolution, soft package structure some top grades, that have particular requirement, and common solvent-free sizing agent does not also reach corresponding requirements at present.While being acid, alkali, the medium such as peppery, salty such as content, composite soft packaging goods easily cause the low even delamination of stripping strength, affect the problems such as normal use of flexible package product.
Summary of the invention
The object 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 there is high anti-hydrolytic performance, and then there is high anti-dielectric behavior, anti-matter requirement in the time of can solving current common solvent-free sizing agent and cannot meet content for acid, alkali, the medium such as peppery, salty, easily causes the problem of the low even delamination of stripping strength.
The object 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 nano-silicon dioxide modified polyester polyol and polyether glycol.
Embodiment of the present invention also provides a kind of preparation method of solvent free bi-component polyurethane adhesive, and the method comprises:
By formula of the present invention, get nano-silicon dioxide modified polyester polyol, polyisocyanates and the polyether glycol of preparation A component, and nano-silicon dioxide modified polyester polyol and the polyether glycol of preparation B component:
Preparation A component: nano-silicon dioxide modified polyester polyol, polyether glycol are added to reactor, mix at 30～50 ℃ 1 hour, add polyisocyanates, react at 70～80 ℃ 3～4 hours, be down to normal temperature and obtain A component;
Preparation B component: nano-silicon dioxide modified polyester polyol and polyether glycol are added to reactor, mix at 30～50 ℃ 1 hour, be down to normal temperature and obtain B component;
A component and this solvent free bi-component polyurethane adhesive of B component mix proportion.
By the above-mentioned technical scheme providing, can be found out, in embodiment of the present invention, use A, B component to form tackiness agent, and 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, B component is the mixture of the polyvalent alcohol of a kind of modification of being mixed by nano-silicon dioxide modified polyester polyol and polyether glycol.Owing to all adopting nano-silicon dioxide modified polyester polyol in A component and B component, by 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 there is high anti-hydrolytic performance, and then there is high anti-dielectric behavior.And the introducing due to nano silicon, also can improve intensity, toughness and the thermotolerance of glue-line, thereby when making this tackiness agent there is high resistance dielectric behavior, also there is good anti-hydrolytic performance, and this tackiness agent does not have the pollution of solvent, can in composite soft packaging field, there is the wider scope of application.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to protection scope of the present invention.
The embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive, and this tackiness agent is comprised of A component and B component;
Wherein, 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; B component is mixed by nano-silicon dioxide modified polyester polyol and polyether glycol, is a kind of mixture of polyvalent alcohol of modification;
A component and B component Ke An functional group mol ratio are: this tackiness agent of-NCO:-OH=1.2～1.8:1.0 mix proportion.
In above-mentioned tackiness agent, the nano-silicon dioxide modified polyester polyol in A component accounts for 10～40% of A component gross weight, and the NCO% content of A component is 9%～21%, and preferably the NCO% content of A component is 11%～18%.
Nano-silicon dioxide modified polyester polyol in 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 nano-silicon dioxide modified polyester polyol in A component and B component, nanometer titanium dioxide silicone content is 5～30% of polyester polyol weight, be preferably 10～20%, the polyester polyol in 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, under ultrasonic wave (ultrasonic frequency is 20 ± 2KHz) and powerful dispersion machine (stirring velocity is 1200rpm) acting in conjunction, disperse 1 hour, the small molecules polyprotonic acid that makes described small molecules polyvalent alcohol and polyester polyol is by functional group's mol ratio :-OH:-COOH=(1.2～1.6): 1 reacts, make nano-silicon dioxide modified polyester polyol.
The small molecules polyprotonic acid that polyester polyol in nano-silicon dioxide modified polyester polyol in above-mentioned A component adopts can be selected from: at least one in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride;
The small molecules polyvalent alcohol that polyester polyol in nano-silicon dioxide modified polyester polyol in 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 one in 6-hexylene glycol, cyclohexanedimethanol, glycerine, TriMethylolPropane(TMP).
The small molecules polyprotonic acid that polyester polyol in nano-silicon dioxide modified polyester polyol in A component and B component adopts can be selected from: at least one in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride.
Polyisocyanates in 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 one in polyether-modified MDI (U-MDI), charing diimine modification MDI (C-MDI), poly methylene poly phenyl poly isocyanate (polymeric MDI claims again PAPI), isophorone diisocyanate (IPDI).
Polyether glycol in above-mentioned tackiness agent A component is selected from:
At least one in the polytetrahydrofuran diol that molecular-weight average is 400～2000 polyoxypropyleneglycol, molecular-weight average is 1000～2000.
The consumption of the polyether glycol in above-mentioned tackiness agent B component be account for B component gross weight 10～50% time, it is 400～2000 polyoxytrimethylene triol that polyether glycol can adopt separately molecular-weight average.
The consumption of the polyether glycol in above-mentioned tackiness agent B component be account for B component gross weight 10～70% time, polyether glycol can adopt with lower arbitrary group:
(1) polytetrahydrofuran diol that the polyoxytrimethylene triol that polyether glycol is 400～2000 by molecular-weight average, the polyoxypropyleneglycol that molecular-weight average is 400～2000 and molecular-weight average are 1000～2000 forms, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in B component is 8～50%, molecular-weight average is that the weight ratio that 400～2000 polyoxypropyleneglycol accounts for B component is 1～10%, and the weight ratio that the polytetrahydrofuran diol that molecular-weight average is 1000～2000 accounts for B component is 1～10%;
(2) polyoxypropyleneglycol that the polyoxytrimethylene triol that polyether glycol is 400～2000 by molecular-weight average and molecular-weight average are 400～2000 forms, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in B component is 9～50%, and the weight ratio that the polyoxypropyleneglycol that molecular-weight average is 400～2000 accounts for B component is 1～20%;
(3) polytetrahydrofuran diol that the polyoxytrimethylene triol that polyether glycol is 400～2000 by molecular-weight average and molecular-weight average are 1000～2000 forms, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in B component is 9～50%, and the weight ratio that the polytetrahydrofuran diol that molecular-weight average is 1000～2000 accounts for B component is 1～20%.
The embodiment of the present invention also provides a kind of preparation method of solvent free bi-component polyurethane adhesive, and the method comprises the following steps:
By above-mentioned formula, get nano-silicon dioxide modified polyester polyol, polyisocyanates and the polyether glycol of preparation A component, and nano-silicon dioxide modified polyester polyol and the polyether glycol of preparation B component:
Preparation A component: nano-silicon dioxide modified polyester polyol, polyether glycol are added to reactor, at 30～50 ℃, mix 1 hour, add polyisocyanates, at 70～80 ℃, react 3～4 hours, being down to normal temperature and obtaining A component, is a kind of affixture of isocyanic ester of modification;
Preparation B component: nano-silicon dioxide modified polyester polyol and polyether glycol being added to reactor, mix 1 hour at 30～50 ℃, be down to normal temperature and obtain B component, is a kind of mixture of polyvalent alcohol of modification;
A component and this solvent free bi-component polyurethane adhesive of B component mix proportion, A component and B component Ke An functional group mol ratio are: this tackiness agent of-NCO:-OH=1.2～1.8:1.0 mix proportion.
The embodiment of the present invention 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 there is high anti-hydrolytic performance, and then there is 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, such as content is the high-grade packing articles of acid, alkali, the medium such as peppery, salty, thereby there is wider Application Areas in composite soft packaging field.
For ease of understanding, below in conjunction with specific embodiment, implementation process of the present invention is described further.
Embodiment mono-
The embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive, this tackiness agent is comprised of A, B component, wherein, 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; B component is mixed by nano-silicon dioxide modified polyester polyol and polyether glycol, is a kind of mixture of polyvalent alcohol of modification;
A component and B component Ke An functional group mol ratio are: this tackiness agent of-NCO:-OH=1.6:1.0 mix proportion.
The preparation method of this tackiness agent, comprises the following steps:
One, preparation A component:
(1) can first prepare 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 filling a prescription (being 1mol glycol ether and 0.3mol1,6-hexylene glycol) mix, and form small molecules polyol blends;
38g nanometer grade silica is joined in above-mentioned small molecules polyol blends, and under ultrasonic wave and powerful dispersion machine acting in conjunction, powerful dispersion 1 hour, forms nano-silicon dioxide modified small molecules polyvalent alcohol;
In pet reaction still, add 0.8mol hexanodioic acid and 0.2mol m-phthalic acid, then add above-mentioned nano-silicon dioxide modified small molecules polyvalent alcohol, fasten feeding cover, heat temperature raising, starts stirring after material melting, passes into nitrogen; Temperature in the kettle reaches about 130 ℃ and starts water outlet, controls 100～102 ℃ of fractionation tower temperatures, continues reacting by heating still, and temperature in the kettle reaches 230 ℃ of left and right and gone out theoretical water.After water outlet completes, insulation 2h, stops passing into nitrogen;
Sampling and testing acid number, controls acid number below 25; Insulation 220-230 ℃ in still, starts progressively to vacuumize, and tests hydroxyl value and acid number, and hydroxyl value reaches 112 ± 6, and acid number 0.3-1 is qualified; 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 polyoxypropyleneglycols that molecular-weight average is 1000,5 parts of polytetrahydrofuran diols that molecular-weight average is 1000,55 parts of MDI;
(2) preparation process:
By 20 parts of nano-silicon dioxide modified polyester polyols, 20 parts of polyoxypropyleneglycols that molecular-weight average is 1000, the polytetrahydrofuran diol that 5 parts of molecular-weight average are 1000 adds in reactor, at 30 ℃, mix 1 hour, add 55 parts of MDI, at 80 ℃, react 4 hours, be down to normal temperature and obtain A component.Test A component NCO%=14.68%.
Two, preparation B component:
(1) can first prepare nano-silicon dioxide modified polyester polyol, comprise:
(1) get 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: preparation method can prepare the step of preparing nano-silicon dioxide modified polyester polyol in A component with reference to this embodiment, 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 polyoxypropyleneglycols that molecular-weight average is 400,20 parts of polyoxytrimethylene triols that molecular-weight average is 400,75 parts of nano-silicon dioxide modified polyester polyols prepared by above-mentioned 2.1.2;
(2) synthetic B component: the polyoxypropyleneglycol that is 400 by 5 parts of molecular-weight average, 20 parts of polyoxytrimethylene triols that molecular-weight average is 400,75 parts of nano-silicon dioxide modified polyester polyols, join in reactor, at 50 ℃, mix 1 hour, be down to normal temperature and obtain B component;
Three, A component and B component coordinate by functional group's mol ratio-NCO:-OH=1.6:1.0, and multiple film forms this tackiness agent.With film formed this tackiness agent printing PET/AL/COEX again, 40 degree slaking 48h, test heat-resisting water stability and resistance to fruit juice stability, test result is as follows: before dress hot water and hot fruit juice, stripping strength is 4.6N/15mm, and hot filling hot water is after 48h, and stripping strength is 4.2～4.6N/15mm; Hot filling fruit juice is after 48h, and stripping strength is 3.9～4.3N/15mm.
Embodiment bis-
The embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive, this tackiness agent is comprised of A, B component, wherein, 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; B component is mixed by nano-silicon dioxide modified polyester polyol and polyether glycol, is a kind of mixture of polyvalent alcohol of modification;
A component and B component Ke An functional group mol ratio are: this tackiness agent of-NCO:-OH=1.55:1.0 mix proportion.
The preparation method of this tackiness agent, comprises the following steps:
One, preparation A component:
(1) first prepare nano-silicon dioxide modified polyester polyol, comprising:
(1) get 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 preparing the step of preparing nano-silicon dioxide modified polyester polyol in A component in embodiment mono-;
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 polyoxypropyleneglycols that molecular-weight average is 2000,17 parts of polyoxypropyleneglycols that molecular-weight average is 400,23 parts of MDI, 25 parts of blending MDI, 5 parts of PAPI;
(2) preparation process:
The polyoxypropyleneglycol that the polyoxypropyleneglycol that is 2000 by 15 parts of above-mentioned nano-silicon dioxide modified polyester polyols, 15 parts of molecular-weight average, 17 parts of molecular-weight average are 400 adds in reactor, at 30 ℃, mix 1 hour, add 23 parts of MDI, 25 parts of blending MDI, 5 parts of PAPI, at 80 ℃, react 4 hours, be down to normal temperature and obtain A component.Test A component NCO%.
Two, preparation B component:
(1) first prepare 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 make nano-silicon dioxide modified polyester polyol with reference to preparing the step of preparing nano-silicon dioxide modified polyester polyol in A component in embodiment mono-, test hydroxyl value;
(2) synthetic B component:
(1) get the raw materials ready: 30 parts of polyoxytrimethylene triols that molecular-weight average is 700, nano-silicon dioxide modified polyester polyol prepared by 70 parts of above-mentioned steps (2);
(2) synthetic B component: the polyoxytrimethylene triol that is 700 by 30 parts of molecular-weight average, 70 parts of nano-silicon dioxide modified polyester polyols prepared by above-mentioned 2.1.2, join in reactor, at 50 ℃, mix 1 hour, be down to normal temperature and obtain B component;
Three, A component and B component coordinate 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 resistance to fruit juice stability, test result is as follows: before dress hot water and hot fruit juice, stripping strength is 4.8N/15mm, and hot filling hot water is after 48h, and stripping strength is 4.4-4.7N/15mm; Hot filling fruit juice is after 48h, and stripping strength is 4.1-4.4N/15mm.
Embodiment tri-
The embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive, this tackiness agent is comprised of A, B component, wherein, 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; B component is mixed by nano-silicon dioxide modified polyester polyol and polyether glycol, is a kind of mixture of polyvalent alcohol of modification;
A component and B component Ke An functional group mol ratio are: 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) get 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 make nano-silicon dioxide modified polyester polyol with reference to preparing the step of preparing nano-silicon dioxide modified polyester polyol in A component in embodiment mono-, 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 polyoxypropyleneglycols that molecular-weight average is 1000,9 parts of polytetrahydrofuran diols that molecular-weight average is 1000,20 parts of CMDI, 25 parts of blending MDI, 3 parts of IPDI.
(2) preparation process:
The polytetrahydrofuran diol that the polyoxypropyleneglycol that is 1000 by 30 parts of above-mentioned nano-silicon dioxide modified polyester polyols, 13 parts of molecular-weight average, 9 parts of molecular-weight average are 1000 adds in reactor, at 40 ℃, mix 1 hour, add 20 parts of C-MDI, 25 parts of blending MDI, 3 parts of IPDI, at 80 ℃, react 4 hours, be down to normal temperature and obtain A component.Test A component NCO%.
Two, preparation B component:
(1) prepare nano-silicon dioxide modified polyester polyol, comprising:
(1) get 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 make nano-silicon dioxide modified polyester polyol with reference to preparing the step of preparing nano-silicon dioxide modified polyester polyol in A component in embodiment mono-, test hydroxyl value;
(2) synthetic B component:
(1) get the raw materials ready: 25 parts of polyoxytrimethylene triols that molecular-weight average is 1000, nano-silicon dioxide modified polyester polyol prepared by 75 parts of above-mentioned steps (2);
(2) synthetic B component: the polyoxytrimethylene triol that is 1000 by 25 parts of molecular-weight average, 75 parts of nano-silicon dioxide modified polyester polyols prepared by above-mentioned 2.1.2, join in reactor, at 50 ℃, mix 1 hour, be down to normal temperature and obtain B component.
Three, A component and B component coordinate 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 resistance to fruit juice stability, test result is as follows: before dress hot water and hot fruit juice, stripping strength is 5.6N/15mm, and hot filling hot water is after 48h, and stripping strength is 5.1-5.4N/15mm; Hot filling fruit juice is after 48h, and stripping strength is 4.6-5.0N/15mm.
The above; be only the present invention's embodiment preferably, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in 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 (6)
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 nano-silicon dioxide modified polyester polyol and polyether glycol;
Nano-silicon dioxide modified polyester polyol in 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 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 nano-silicon dioxide modified polyester polyol in described A component and B component, 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, the ultrasonic wave that is 20 ± 2KHz in ultrasonic frequency and stirring velocity are to disperse 1 hour under the powerful dispersion machine acting in conjunction of 1200rpm, the small molecules polyprotonic acid that makes described small molecules polyvalent alcohol and polyester polyol is by functional group's mol ratio :-OH:-COOH=1.2～1.6:1.0 reacts, and makes nano-silicon dioxide modified polyester polyol.
2. tackiness agent according to claim 1, it is characterized in that, the small molecules polyprotonic acid that the polyester polyol in the nano-silicon dioxide modified polyester polyol in described A component adopts is selected from: at least one in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride;
The small molecules polyvalent alcohol that polyester polyol in nano-silicon dioxide modified polyester polyol in 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 one in 6-hexylene glycol, cyclohexanedimethanol, glycerine, TriMethylolPropane(TMP);
The small molecules polyprotonic acid that polyester polyol in nano-silicon dioxide modified polyester polyol in described A component and B component adopts is selected from: at least one in hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride.
3. tackiness agent according to claim 1, is characterized in that, the polyisocyanates in described A component is selected from:
Ditan-2, the part by weight of 4 '-vulcabond is more than or equal to 25% ditan-4,4 '-vulcabond and ditan-2, the mixture of 4 '-vulcabond, ditan-4, at least one in 4 '-vulcabond, polyether-modified MDI, Carbodiimide-Modified MDI, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate.
4. tackiness agent according to claim 1 and 2, is characterized in that,
Polyether glycol in described A component is selected from: at least one in the polytetrahydrofuran diol that the polyoxypropyleneglycol that molecular-weight average is 400～2000, molecular-weight average are 1000～2000;
The consumption of the polyether glycol in described B component be account for B component gross weight 10～50% time, polyether glycol adopts the polyoxytrimethylene triol that molecular-weight average is 400～2000.
5. tackiness agent according to claim 1, is characterized in that, the consumption of the polyether glycol in described B component be account for B component gross weight 10～70% time, polyether glycol adopts with lower arbitrary group:
(1) polytetrahydrofuran diol that the polyoxypropyleneglycol that the polyoxytrimethylene triol that is 400～2000 by molecular-weight average, molecular-weight average are 400～2000 and molecular-weight average are 1000～2000 forms, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in B component is 8～50%, molecular-weight average is that the weight ratio that 400～2000 polyoxypropyleneglycol accounts for B component is 1～10%, and the weight ratio that the polytetrahydrofuran diol that molecular-weight average is 1000～2000 accounts for B component is 1～10%;
(2) polyoxypropyleneglycol that the polyoxytrimethylene triol that is 400～2000 by molecular-weight average and molecular-weight average are 400～2000 forms, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in B component is 9～50%, and the weight ratio that the polyoxypropyleneglycol that molecular-weight average is 400～2000 accounts for B component is 1～20%;
(3) polytetrahydrofuran diol that the polyoxytrimethylene triol that is 400～2000 by molecular-weight average and molecular-weight average are 1000～2000 forms, wherein, molecular-weight average is that the weight ratio that 400～2000 polyoxytrimethylene triol accounts in B component is 9～50%, and the weight ratio that the polytetrahydrofuran diol that molecular-weight average is 1000～2000 accounts for B component is 1～20%.
6. a preparation method for solvent free bi-component polyurethane adhesive, is characterized in that, the method comprises:
By the formula of claim 1, get nano-silicon dioxide modified polyester polyol, polyisocyanates and the polyether glycol of preparation A component, and nano-silicon dioxide modified polyester polyol and the polyether glycol of preparation B component:
Preparation A component: nano-silicon dioxide modified polyester polyol, polyether glycol are added to reactor, mix at 30～50 ℃ 1 hour, add polyisocyanates, react at 70～80 ℃ 3～4 hours, be down to normal temperature and obtain A component;
Preparation B component: nano-silicon dioxide modified polyester polyol and polyether glycol are added to reactor, mix at 30～50 ℃ 1 hour, be down to normal temperature and obtain B component;
A component and this solvent free bi-component polyurethane adhesive of B component mix proportion.
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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 |
| CN111395011B (en) * | 2020-05-21 | 2022-03-29 | 烟台同兴过滤科技有限公司 | Filter cloth gluing process |
| CN112301505B (en) * | 2020-10-16 | 2022-03-22 | 高梵(浙江)信息技术有限公司 | Seamless down-filled down jacket fabric and production method thereof |
| CN114316243B (en) * | 2021-12-29 | 2023-12-12 | 山东一诺威新材料有限公司 | Silica 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 |
| CN116217876A (en) * | 2023-03-27 | 2023-06-06 | 南通高盟新材料有限公司 | High-barrier heat-resistant solvent-free polyurethane composite material and preparation method thereof |
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