CN103013417B - Solvent-free double-constituent polyurethane compound adhesive and preparation method for same - Google Patents
Solvent-free double-constituent polyurethane compound adhesive and preparation method for same Download PDFInfo
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- CN103013417B CN103013417B CN201210516688.XA CN201210516688A CN103013417B CN 103013417 B CN103013417 B CN 103013417B CN 201210516688 A CN201210516688 A CN 201210516688A CN 103013417 B CN103013417 B CN 103013417B
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Abstract
The invention provides a solvent-free double-constituent polyurethane adhesive which is composed of a constituent A and a constituent B, wherein the constituent A is end isocyanate-group polyurethane prepolymer, and the constituent B is carboxyl-containing polyether polyol. The solvent-free polyurethane adhesive is strong in compounding fastness, long in service usage period and wide in suitable base material range; and moreover, the compound film prepared from the adhesive can still keep an excellent appearance and excellent adhesion property after high-temperature sterilization treatment.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of solvent-free dual-component polyurethane adhesive and preparation method thereof.
Technical background
Current, China's food flexible packing is mostly bonding as main take solvent-based adhesive with composite membrane, adopts composite dry process to carry out compound, and because recombination process energy consumption is high, VOC discharge is large, has the problems such as dissolvent residual, serious threat food safety.Solvent-free polyurethane adhesive, because solid content is high, uses safety, environmental protection, by the inexorable trend that is the development of packing recombining process.
Solvent-free composite adhesive, comprises two types of one-component polyurethane adhesive and dual-component polyurethane adhesives.Because the one's share of expenses for a joint undertaking amount of solventless adhesive is far smaller than solvent-based adhesive, and there is the many factors such as wettability is poor, so in the time being used for the bonding composite membrane containing tinsels such as aluminium foils, can exist after High Temperature Sterilization, compound fastness obviously weakens, and the problems such as colloid flavescence impact is attractive in appearance, show poor high thermal resistance and weather resistance.In addition, existing dual-component polyurethane adhesive exists viscosity after two kinds of components mix sharply to rise, and causes the even problem that even cannot be coated with of crawling.
CN1989217B patent documentation discloses a kind of solvent-free polyurethane adhesive with excellent high temperature resistant and weather resistance, but is applicable to the bonding of the tinsels such as aluminium and plastic film, composite base material narrow range.CN101503611A patent documentation discloses a kind of double component solvent-free polyurethane adhesive, shown the performance of low water absorbable, low in hydrolysis, high-impact, but its compound fastness is not strong, and its matrix material does not meet resistant to elevated temperatures requirement.
Summary of the invention
The technical problem that will solve required for the present invention is to provide a kind of solvent-free dual-component polyurethane adhesive and preparation method thereof, and its object is: the first, and applicable base materials is wide, and compound fastness is strong, is particularly carrying out after high-temperature sterilization processing, still keeping good cohesiveness; The second, eliminate the impact that causes crawling even cannot be coated with because viscosity is high after two kinds of components mix, extend the colloid usage period; The 3rd, colloid is inhibited from yellowing, good endurance.
For achieving the above object, the present invention adopts following technical scheme:
Described solvent-free dual-component polyurethane adhesive comprises A, two components of B, and A component is to generate isocyanate terminated based polyurethanes performed polymer by the small molecules polyether glycol of 50%～75% isocyanic ester and 15%～30% and/or 10%～20% plant oil modified polyol reaction; B component is to generate carboxylic polyether glycol by 75%～98% micromolecular polyether glycol and 2%～25% anhydride reaction, retardance catalyzer account for other raw materials in B component gross weight 0.1%～0.3%.
Isocyanic ester in described A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); Small molecules polyether glycol is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; Plant oil modified polyvalent alcohol is that molecular weight is the castor oil modified trivalent alcohol (functionality is 2.7) that 1000 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900.
The preparation method of the isocyanate terminated based polyurethanes performed polymer of above-mentioned A component is: under nitrogen protection, small molecules polyether glycol and/or plant oil modified polyvalent alcohol are heated to 130～150 ℃, under vacuum tightness 0.266KPa, after dehydration 1.5～2h, moisture content is surveyed in sampling, in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, add isocyanic ester in batches, generate base polyurethane prepolymer for use as at 85～90 ℃ of reaction 2～3h;
Micromolecular polyether glycol in described B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; Acid anhydrides for modification is trimellitic acid 1,2-anhydride; Retardance catalyzer is trolamine.
The preparation method of the carboxylic polyether glycol of above-mentioned B component is: small molecules polyether glycol is heated to 150～170 ℃, under vacuum tightness 0.266KPa, after dehydration 1.5～2h, water-content is surveyed in sampling, in the time of water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, at 120～130 ℃, carry out sour modification, add again retardance catalyzer, obtain carboxylic polyether glycol.
In the carboxylic polyether glycol of above-mentioned B component, the content of carboxyl is 4%～12%.
The preparation method of described solvent-free dual-component polyurethane adhesive is: at 30～50 ℃ of temperature, A component and B component are fully mixed by functional group's mol ratio NCO/OH=1.0～1.5.
Below technical scheme of the present invention is described in further detail as follows:
A kind of solvent-free dual-component polyurethane adhesive, comprises A, two components of B, it is characterized in that, A component is isocyanate terminated based polyurethanes performed polymer, and B component is carboxylic polyether glycol; A component and B component are pressed functional group's mol ratio NCO/OH=1.0～1.5, preferably NCO/OH=1.3～1.5.
The raw material weight proportioning of preparing solvent-free polyurethane adhesive of the present invention is:
A component: isocyanic ester 50%～75%,
Small molecules polyether glycol 15%～30%,
Plant oil modified polyvalent alcohol 10%～20%,
B component: small molecules polyether glycol 75%～98%,
Trimellitic acid 1,2-anhydride 2%～25%,
Retardance catalyzer, its content account for other raw materials in B component gross weight 0.1%～0.3%.
Preferably, the raw material weight proportioning of preparing solvent-free polyurethane adhesive of the present invention is:
A component: isocyanic ester 60%～75%,
Small molecules polyether glycol 15%～25%,
Plant oil modified polyvalent alcohol 10%～15%,
B component: small molecules polyether glycol 75%～95%,
Trimellitic acid 1,2-anhydride 5%～25%,
Retardance catalyzer, its content account for other raw materials in B component gross weight 0.1%～0.3%.
Isocyanic ester in A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); Small molecules polyether glycol is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; Plant oil modified polyvalent alcohol is that molecular weight is the castor oil modified trivalent alcohol that 1000 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900.
Small molecules polyether glycol in B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; Acid anhydrides for modification is trimellitic acid 1,2-anhydride; Retardance catalyzer is trolamine.
Through a large amount of experimental studies, when the content of carboxyl in B component is controlled to 4%～12%, be surprised to find that, the compound fastness of solvent-free dual-component polyurethane adhesive of the present invention significantly strengthens, and causes the even detrimentally affect that even cannot be coated with of crawling because viscosity is too high after effectively having eliminated A, the mixing of B component.For proving the impact of different carboxyl-contents on the compound fastness of tackiness agent (this test adopts peeling force to measure compound fastness) and viscosity in B component, contriver has carried out following contrast experiment, and test-results is in table one.Wherein sample 1 is the prepared tackiness agent of embodiment 11, and the preparation method of sample 2,3,4,5,6,7,8, with reference to the method for embodiment 11, is guaranteeing under the prerequisite that other raw materials and reaction conditions are constant, add respectively 10 parts, 12 parts, 14 parts, 22 parts, 41 parts, 55 parts, 58 parts of trimellitic acid 1,2-anhydrides, make carboxyl-content and are respectively 3%, 3.5%, 4%, 6%, 10%, 12.5%, 13% polyether glycol, i.e. above-mentioned sample 2-8.
The impact of carboxyl-content on compound fastness and viscosity in table one, B component
The testing data demonstration of table one, in the time that the content of carboxyl in B component is less than 4%, solventless adhesive peeling force of the present invention is little, and compound fastness is poor; In the time that the content of carboxyl in B component is greater than 12%, the peeling force of solventless adhesive of the present invention is large, and compound fastness is strong, but it is excessive to join initial viscosity after glue, is difficult to evenly be coated with at substrate surface.Hence one can see that, and when the content of carboxyl in B component is 4%～12% time, prepared solventless adhesive of the present invention meets composite demand and modest viscosity, is convenient to even coating, meets the requirement of performance and technique.
The preparation method of above-mentioned solvent-free dual-component polyurethane adhesive, comprises the following steps:
(1) take A, B component by functional group's mol ratio NCO/OH=1.0～1.5, each component takes raw material by following proportioning:
A component: isocyanic ester 50%～75%,
Small molecules polyether glycol 15%～30%,
Plant oil modified polyvalent alcohol 10%～20%,
B component: small molecules polyether glycol 75%～98%,
Trimellitic acid 1,2-anhydride 2%～25%,
Retardance catalyzer, its content account for other raw materials in B component gross weight 0.1%～0.3%.
(2) prepare A component: under the protection of nitrogen, by small molecules polyether glycol and (or) plant oil modified polyvalent alcohol is heated to 130～150 ℃, under vacuum tightness 0.266KPa, after dehydration 1.5～2h, moisture content is surveyed in sampling, in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, add isocyanic ester in batches, generate base polyurethane prepolymer for use as at 85～90 ℃ of reaction 2～3h;
(3) prepare B component: under the protection of nitrogen, small molecules polyether glycol is heated to 150～170 ℃, under vacuum tightness 0.266KPa, after dehydration 1.5～2h, moisture content is surveyed in sampling, in the time of water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, at 120～130 ℃, carry out sour modification, obtain carboxylic polyether glycol;
(4) in B component, add the retardance catalyzer of its raw material gross weight 0.1%～0.3%;
(5) prepare tackiness agent: A component and B component fully mix at 30～50 ℃ of temperature, obtain solvent-free polyurethane adhesive.
The solvent-free dual-component polyurethane adhesive of gained of the present invention can be applicable to comprise the compound of the multiple films such as CPP, PVDC, PE, BOPP, PA, PET, aluminium foil.
Compared with prior art, in the present invention, there is following beneficial effect:
1. dual-component polyurethane adhesive of the present invention is difficult to bonding base material to some and shows excellent cementability, as bonded polyethylene (PE), polypropylene (CPP), aluminium foil etc., and made foil laminated film still keeps good cementability through 121 ℃ of boiling sterilizations are after treatment.
2. after effectively having eliminated A, the mixing of B component, cause the even detrimentally affect that even cannot be coated with of crawling because viscosity is too high, extend the tackiness agent usage period.
3. colloid is inhibited from yellowing, good endurance.
4. solvent-free discharge in production process, pollution-free, safe.
5. reduce production costs, because producing without waste gas, so do not need waste gas exhaust device; Do not need drying tunnel just can reach solidification effect, reduce energy consumption, simplified apparatus; Improve production rate, top speed can reach 500m/min, generally in 300m/min left and right.
6. unit surface glue consumption is little, cost-saving.
Specific implementation method:
In order to further illustrate characteristic of the present invention, be described in further detail below in conjunction with embodiment, but should not be understood as the restriction of protection domain of the present invention.
The preparation of embodiment 1:A-1
Under nitrogen protection; the polyoxytrimethylene triol of the polyoxypropyleneglycol of 65 parts of molecular weight 400,60 parts of molecular weight 300 is heated to 130 ℃; under vacuum tightness 0.266KPa; after dehydration 1.5h, water content is surveyed in sampling; in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, add 150 parts of HMDI, 125 parts of IPDI; at 85 ℃, react 2h, obtain A component (hereinafter to be referred as A-1).
The preparation of embodiment 2:A-2
Under nitrogen protection; the soybean oil modified polyvalent alcohol of the polyoxytrimethylene triol of 120 parts of molecular weight 300,80 parts of molecular weight 1000 (functionality 2.6) is heated to 150 ℃; under vacuum tightness 0.266KPa; after dehydration 2h, water content is surveyed in sampling; in the time of water-content ﹤ 0.05%, be cooled to 60 ℃, add 150 parts of HMDI, 50 parts of IPDI; at 120 ℃, react 2.5h, obtain A component (hereinafter to be referred as A-2).
The preparation of embodiment 3:A-3
Under nitrogen protection; the castor oil modified trivalent alcohol of the polyoxypropyleneglycol of 60 parts of molecular weight 400,40 parts of molecular weight 900 is heated to 140 ℃; under vacuum tightness 0.266KPa; after dehydration 2h, water content is surveyed in sampling; in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, add 200 parts of HMDI, 100 parts of IPDI; at 90 ℃, react 3h, obtain A component (hereinafter to be referred as A-2).
The preparation of embodiment 4:B-1
Under the protection of nitrogen; the polyoxypropyleneglycol of the polyoxytrimethylene triol of 40 parts of molecular weight 300,9 parts of molecular weight 400 is joined in reactor; be heated to 150 ℃ of vacuum hydro-extractions; after dehydration 1.5h, water content is surveyed in sampling; in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, then add 1 part of trimellitic acid 1,2-anhydride; at 120 ℃, carry out sour modification, obtain B component (hereinafter to be referred as B-1).
The preparation of embodiment 5:B-2
Under the protection of nitrogen; the polyoxypropyleneglycol of the polyoxytrimethylene triol of 100 parts of molecular weight 300,90 parts of molecular weight 400 is joined in reactor; be heated to 170 ℃ of vacuum hydro-extractions; after dehydration 2h, water content is surveyed in sampling; in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, add 10 parts of trimellitic acid 1,2-anhydrides; at 125 ℃, carry out sour modification, then add 0.2 part of trolamine to obtain B component.Hereinafter to be referred as B-3.
The preparation of embodiment 6:B-3
Under the protection of nitrogen; the polyoxypropyleneglycol of the polyoxytrimethylene triol of 100 parts of molecular weight 300,50 parts of molecular weight 400 is joined in reactor; be heated to 170 ℃ of vacuum hydro-extractions; after dehydration 2h, water content is surveyed in sampling, in the time of water-content ﹤ 0.05%, is cooled to 70 ℃; add 50 parts of trimellitic acid 1,2-anhydrides; at 130 ℃, carry out sour modification, then add 0.6 part of trolamine, obtain B component.Hereinafter to be referred as B-4.
Embodiment 7: take A-1, B-1 component by the mol ratio NCO/OH=1.0 of functional group, fully mix at 30 ℃, 50 ℃ respectively, measure it and mix the viscosity after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 8: take A-2, B-1 component by the mol ratio NCO/OH=1.2 of functional group, fully mix at 30 ℃, 50 ℃ respectively, measure it and mix the viscosity after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 9: take A-3, B-1 component by the mol ratio NCO/OH=1.3 of functional group, fully mix at 30 ℃, 50 ℃ respectively, measure it and mix the viscosity after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 10: take A-3, B-2 component by the mol ratio NCO/OH=1.4 of functional group, fully mix at 30 ℃, 50 ℃ respectively, measure it and mix the viscosity after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 11: take A-3, B-3 component by the mol ratio NCO/OH=1.5 of functional group, fully mix at 30 ℃, 50 ℃ respectively, measure it and mix the viscosity after 2 minutes, 30 minutes, the results are shown in table two.
Table two, 30 ℃, 50 ℃ are joined the viscosity of glue after 2 minutes and after 30 minutes
Embodiment 12: prepare respectively two kinds of composite membranes with solvent-free dual-component polyurethane adhesive of the present invention (embodiment 8-embodiment 11): BON biaxially oriented nylon film (BOPA, 0.015mm)/low-density polyethylene film (LDPE, 0.035mm) and BON biaxially oriented nylon film (BOPA, 0.015mm)/aluminium foil (0.007mm)/polypropylene casting film (CPP, 0.065mm).Be coated with and be compounded at 30 ℃～50 ℃ and carry out, spread is 1.0g/m
2～2.0g/m
2, then at 50 ℃, slaking, after 48 hours, is cooled to room temperature, composite membrane is cut into wide 15 millimeters, and the test bar of long 200 millimeters, at room temperature measures T-shaped stripping strength with BLD-200 electron detachment trier, and draw speed is 100 in the least m/min.Respectively at 100 ℃, 121 ℃ poach after 30 minutes, then measure after the same method T-shaped stripping strength, the results are shown in table three.In addition, above-mentioned composite membrane is placed more than 4 weeks and observed at 40 ℃, composite membrane still keeps good appearance, does not all occur pears skin, colloid flavescence phenomenon.
The splitting power of table three, mensuration composite membrane
As shown in Table 3, the peeling force between the compound CPP/ aluminium foil of solvent-free polyurethane adhesive prepared by the present invention is 12.5 N/15mm, 121 ℃ of poach after 30 minutes peeling force be 12.0 N/15mm; And the peeling force between CPP/ aluminium foil is 3 N/15mm in the embodiment 13 of patent CN101280167B, 100 ℃ of poach after 30 minutes peeling force be 2.5N/15mm.Hence one can see that, and the prepared solventless adhesive of the present invention has significantly improved the cementability of colloid, and compound fastness is strong.
Comparative example 1: embodiment 7 and the difference of embodiment 8,9 are not add plant oil modified polyvalent alcohol in the A component of embodiment 7, have only used micromolecular polyether glycol.By relatively finding, the initial viscosity of embodiment 8,9 in the time of 30 ℃ is lower, and the initial viscosity of embodiment 7 too high be semi-solid state, thereby need in the time of 50 ℃, can join glue, coating, and colloid initial viscosity is higher.Therefore,, in the time that small molecules polyvalent alcohol coordinates plant oil modified polyvalent alcohol to use, significantly reduced the initial viscosity of solventless adhesive.
Comparative example 2: embodiment 9 is that with the difference of embodiment 10,11 the B component of embodiment 9 does not add retardance catalyzer, and in the B component of embodiment 10,11, all adds the retardance catalyzer of different ratios.By relatively finding, substantially curing when embodiment 9 prepares glue 30 minutes, and embodiment 10,11 still keeps low viscosity state in the time preparing after glue 30 minutes.Further measure, the made solvent-free glue of embodiment 10,11, at 45 minutes after fixing, has improved the mobility of reaction mass, has extended the usage period of colloid.
Claims (2)
1. a solvent-free dual-component polyurethane adhesive, it is characterized in that, described solvent-free dual-component polyurethane adhesive comprises A, two components of B, and A component is to be reacted the isocyanate terminated based polyurethanes performed polymer generating with 15% polyoxypropyleneglycol, 10% castor oil modified trivalent alcohol by 50%HMDI, 25%IPDI; B component is to generate carboxylic polyether glycol by the trimellitic acid anhydride reactant of 50% polyoxytrimethylene triol, 25% polyoxypropyleneglycol and 25%, retardance catalyzer trolamine account for other raw materials in B component gross weight 0.3%; A component and B component are fully mixed by the mol ratio NCO/OH=1.5 of functional group;
The molecular weight of described polyoxypropyleneglycol is 400; The molecular weight of castor oil modified trivalent alcohol is 900; The molecular weight of polyoxytrimethylene triol is 300.
2. the preparation method of solvent-free dual-component polyurethane adhesive according to claim 1, is characterized in that:
(1) prepare the isocyanate terminated based polyurethanes performed polymer of A component: under nitrogen protection, polyoxypropyleneglycol and castor oil modified trivalent alcohol are heated to 140 ℃, under vacuum tightness 0.266KPa, after dehydration 2h, moisture content is surveyed in sampling, in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, add HMDI, IPDI in batches, generate base polyurethane prepolymer for use as at 90 ℃ of reaction 3h;
(2) prepare the carboxylic polyether glycol of B component: polyoxytrimethylene triol, polyoxypropyleneglycol are heated to 170 ℃, under vacuum tightness 0.266KPa, after dehydration 2h, water-content is surveyed in sampling, in the time of water-content ﹤ 0.05%, be cooled to 70 ℃, then add trimellitic acid 1,2-anhydride, at 130 ℃, carry out sour modification, add again retardance catalyzer trolamine, obtain carboxylic polyether glycol;
(3) A component and B component are fully mixed by the mol ratio NCO/OH=1.5 of functional group.
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| CN103897653B (en) | 2015-12-30 |
| CN103897653A (en) | 2014-07-02 |
| CN103013417A (en) | 2013-04-03 |
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Effective date of registration: 20151214 Address after: 215513 Jiangsu Province Economic and Technological Development Zone of Changshou City Science Park Patentee after: Suzhou Bolaite New Material Co.,Ltd. Address before: 215534 Dong Zhou road, Changshu national economic and Technological Development Zone, Suzhou, Jiangsu Patentee before: Changshu Guohe New Materials Co., Ltd. |