CN102994035B - Solvent-free polyurethane adhesive coated at normal temperature and preparation method thereof - Google Patents
Solvent-free polyurethane adhesive coated at normal temperature and preparation method thereof Download PDFInfo
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- CN102994035B CN102994035B CN201210516125.0A CN201210516125A CN102994035B CN 102994035 B CN102994035 B CN 102994035B CN 201210516125 A CN201210516125 A CN 201210516125A CN 102994035 B CN102994035 B CN 102994035B
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Abstract
The invention provides a solvent-free polyurethane adhesive coated at normal temperature. The solvent-free polyurethane adhesive comprises a component A and a component B, wherein the component A is an isocyanate-terminated polyurethane prepolymer and the component B is a carboxyl-containing polyether polyol. The solvent-free polyurethane adhesive can be coated at the normal temperature, and has the advantages of long usage period, strong compound fastness and a wide range of applicable base materials; and furthermore, a compound film prepared by the solvent-free polyurethane adhesive can still keep excellent appearance and adhesion after high-temperature sterilization treatment.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of normal temperature coating solvent-free polyurethane adhesive and preparation method thereof.
Technical background
Current, China's food flexible packing is mostly bonding as main take solvent-borne type composite gum 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.No-solvent polyurethane composite gum, because solid content is high, is used safety, environmental protection, by the inexorable trend that is the development of packing recombining process.
No-solvent polyurethane composite gum, comprises two types of monocomponent polyurethane composite gum and dual-component polyurethane composite gum.Because the one's share of expenses for a joint undertaking amount of no-solvent type composite gum is far smaller than solvent-borne type composite gum, and have 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.In addition, existing dual-component polyurethane composite gum 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 no-solvent polyurethane composite gum with excellent high temperature resistant and weather resistance, is mainly applicable to the bonding of the tinsels such as aluminium and plastic film, composite base material narrow range, and coating temperature high (more than 35 ℃).CN101503611A patent documentation discloses a kind of double component solvent-free polyurethane composite gum, 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 composite gum 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, effectively reduce coating temperature, reduce energy consumption.
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 the isocyanate terminated based polyurethanes performed polymer being generated by the plant oil modified polyol reaction of the small molecules polyether glycol of 50%～75% isocyanic ester and 15%～30% and/or 10%～20%; B component is the carboxylic polyether glycol being generated by the anhydride reaction of 75%～98% micromolecular polyether glycol and 2%～25%, solidifying agent account for other raw materials in B component gross weight 0.1%～0.3%.
Isocyanic ester in above-mentioned 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, 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;
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; Solidifying agent is 2-ethyl-4-methylimidazole.
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 solidifying agent, 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 15～20 ℃ 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 normal temperature coating no-solvent polyurethane composite gum, 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 no-solvent polyurethane composite gum 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%,
Solidifying agent, its content account for other raw materials in B component gross weight 0.1%～0.3%.
Preferably, the raw material weight proportioning of preparing no-solvent polyurethane composite gum 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%,
Solidifying agent, 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 be molecular weight 400 polyoxypropyleneglycol 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; Solidifying agent is that 2-ethyl-4 Methylimidazole, glyoxal ethyline, butyl-glyoxal ethyline are in the ratio mixing of 2:1:1.
Through a large amount of experimental studies, when the content of carboxyl in B component is controlled to 4%～12%, be surprisingly found out that, the compound fastness of no-solvent polyurethane composite gum 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 composite gum (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 composite gum 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, can meet composite demand, 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, composite performance optimum and the modest viscosity of prepared solventless adhesive of the present invention, be convenient to even coating.
The preparation method of above-mentioned solvent-free dual-component polyurethane composite gum, comprises the following steps:
(1) by functional group's mol ratio NCO/OH=1.0～1.5, take A, B component, 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%,
Solidifying agent, 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, 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;
(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 solidifying agent of its raw material gross weight 0.1%～0.3%;
(5) prepare composite gum: A component and B component be by functional group's mol ratio NCO/OH=1.0～1.5, at 15～20 ℃ of temperature, fully mix, obtain no-solvent polyurethane composite gum.
The solvent-free dual-component polyurethane composite gum 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 composite gum 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. effectively eliminated after A, B component mix and caused the even detrimentally affect that even cannot be coated with of crawling because viscosity is too high, extended composite gum working life.
3. significantly reduce solidification value, shorten set time.
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 polyoxypropyleneglycol of 125 parts of molecular weight 400 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 70 ℃, add 150 parts of HMDI, 50 parts of IPDI; at 90 ℃, 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 60 ℃, 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%, is cooled to 60 ℃; add 10 parts of trimellitic acid 1,2-anhydrides; at 125 ℃, carry out sour modification, then add 0.1 part of 2-ethyl-4 Methylimidazole, 0.05 part of glyoxal ethyline, 0.05 part of butyl-glyoxal ethyline, 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 60 ℃; add 50 parts of trimellitic acid 1,2-anhydrides; at 130 ℃, carry out sour modification, then add 0.03 part of 2-ethyl-4 Methylimidazole, 0.015 part of glyoxal ethyline, 0.015 part of butyl-glyoxal ethyline, 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 of functional group, fully mix at 15 ℃, 20 ℃ 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 15 ℃, 20 ℃ 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 15 ℃, 20 ℃ 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 15 ℃, 20 ℃ 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 15 ℃, 20 ℃ respectively, measure it and mix the viscosity after 2 minutes, 30 minutes, the results are shown in table two.
Table two, 15 ℃, 20 ℃ are joined the viscosity of glue after 2 minutes and after 30 minutes
Embodiment 12: prepare respectively two kinds of composite membranes by solvent-free dual-component polyurethane composite gum 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 15～20 ℃ 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.In addition, 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
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 (polyoxypropyleneglycol, polyoxytrimethylene triol).By relatively finding, the initial viscosity of embodiment 8,9 in the time of 15 ℃ of normal temperature is lower, and the initial viscosity of embodiment 7 in the time of 15 ℃ is too high, has a strong impact on Painting effect.Therefore,, in the time that small molecules polyvalent alcohol coordinates plant oil modified polyvalent alcohol to use, significantly reduced the initial viscosity of solvent-free composite gum.
Comparative example 2: embodiment 9 is that with the difference of embodiment 10,11 the B component of embodiment 9 does not add solidifying agent, and in the B component of embodiment 10,11, all adds the solidifying agent of different ratios.By relatively finding, embodiment 9 15 ℃, 20 ℃ join glue after 30 minutes still in liquid state, affect surface covered, need improve solidification value; And that embodiment 10,11 joins glue at 15 ℃ is curing after 30 minutes, learn that thus the solidifying agent that is added into suitable proportion has greatly reduced solidification value.
Claims (6)
1. a normal temperature coating solvent-free polyurethane adhesive, it is characterized in that, described normal temperature coating solvent-free polyurethane adhesive comprises A, two components of B, and A component is the isocyanate terminated based polyurethanes performed polymer with the plant oil modified polyol reaction generation of 15%～30% small molecules polyether glycol and 10%～20% by 50%～75% isocyanic ester; B component is the polyether glycol that the carboxyl-content that generated by the anhydride reaction of 75%～98% micromolecular polyether glycol and 2%～25% is 4%～12%, solidifying agent account for other raw materials in B component gross weight 0.1%～0.3%.
2. normal temperature coating solvent-free polyurethane adhesive as claimed in claim 1, is characterized in that, the isocyanic ester in A component is dicyclohexyl methane diisocyanate 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 that 1000 functionality are that 2.6 epoxy soybean oil modified polyalcohol and/or molecular weight are that 900 functionality are 2.7 castor oil modified trivalent alcohol.
3. normal temperature coating solvent-free polyurethane adhesive as claimed in claim 1 or 2; it is characterized in that; the preparation method of the isocyanate terminated based polyurethanes performed polymer of 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.
4. normal temperature coating solvent-free polyurethane adhesive as claimed in claim 1, is characterized in that, the micromolecular 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; Solidifying agent is 2-ethyl-4-methylimidazole.
5. the coating of the normal temperature as described in claim 1 or 4 solvent-free polyurethane adhesive, it is characterized in that, the preparation method of the carboxylic polyether glycol of B component is: small molecules polyether glycol is heated to 150～170 ℃, and 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 solidifying agent, obtain carboxylic polyether glycol.
6. normal temperature coating solvent-free polyurethane adhesive as claimed in claim 1, it is characterized in that, the preparation method of normal temperature coating solvent-free polyurethane adhesive is: at 15～20 ℃ of temperature, A component and B component are fully mixed by functional group's mol ratio NCO/OH=1.0～1.5.
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| CN103555429B (en) * | 2013-11-05 | 2016-01-20 | 湖北大学 | A kind of preparation method of carboxylic hydrogenated castor oil polyalcohol |
| CN104449538B (en) * | 2014-12-04 | 2016-09-07 | 上海康达化工新材料股份有限公司 | The double component solvent-free polyurethane structure glue of normal temperature coating and its preparation method and application method |
| CN105802189A (en) * | 2016-04-06 | 2016-07-27 | 苏州甫众塑胶有限公司 | Composite natural gas pipeline connector material and preparation method thereof |
| CN107814902B (en) * | 2017-11-06 | 2020-04-10 | 万华化学集团股份有限公司 | Hydroxyl-containing polyurethane aqueous dispersion and preparation method and application thereof |
| CN108215366A (en) * | 2017-12-29 | 2018-06-29 | 三星聚合物有限公司 | Solventfree resin and preparation method thereof, reagent preparation box and application |
| CN108559440B (en) * | 2018-04-27 | 2021-12-14 | 上海回天新材料有限公司 | High-speed compounding and quick curing solvent-free polyurethane laminating adhesive as well as preparation method and application thereof |
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