CN102994035A - 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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- CN102994035A CN102994035A CN2012105161250A CN201210516125A CN102994035A CN 102994035 A CN102994035 A CN 102994035A CN 2012105161250 A CN2012105161250 A CN 2012105161250A CN 201210516125 A CN201210516125 A CN 201210516125A CN 102994035 A CN102994035 A CN 102994035A
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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 the solvent-borne type composite gum with composite membrane, and it is compound to adopt composite dry process to carry out, because the recombination process energy consumption is high, the VOC discharging is large, the problems such as dissolvent residual is arranged, the serious threat food safety.The no-solvent polyurethane composite gum is used safety, environmental protection because solid content is high, will be the inexorable trend of packing recombining process development.
The 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 the solvent-borne type composite gum, and have the poor many factors that waits of wettability, thus when for the bonding composite membrane that contains the tinsel such as aluminium foil, can have High Temperature Sterilization after, compound fastness obviously weakens.In addition, existing dual-component polyurethane composite gum existence viscosity after two kinds of components mix sharply rises, and causes the problem that crawling is even even can't be coated with.
The CN1989217B patent documentation discloses a kind of no-solvent polyurethane composite gum with excellent high temperature resistant and weather resistance, mainly is applicable to the bonding of the tinsel such as aluminium and plastic film, composite base material narrow range, and coating temperature height (more than 35 ℃).The 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 satisfy resistant to elevated temperatures requirement.
Summary of the invention
The technical problem that will solve required for the present invention provides a kind of solvent-free dual-component polyurethane composite gum and preparation method thereof, and its purpose is: the first, and applicable base materials is wide, and compound fastness is strong, is particularly carrying out still keeping good cohesiveness after high-temperature sterilization is processed; The second, eliminate two kinds of components and mix the impact that causes crawling even can't be coated with because of the viscosity height afterwards, prolong 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 two components of A, B, and the A component is the isocyanate terminated based polyurethanes performed polymer that the plant oil modified polyol reaction by the small molecules polyether glycol of 50%～75% isocyanic ester and 15%～30% and/or 10%～20% generates; The B component is the carboxylic polyether glycol that the anhydride reaction by 75%～98% micromolecular polyether glycol and 2%～25% generates, solidifying agent account for other raw materials in the B component gross weight 0.1%～0.3%.
Isocyanic ester in the above-mentioned A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); The 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 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900 castor oil modified trivalent alcohol (functionality is 2.7).
The preparation method of the isocyanate terminated based polyurethanes performed polymer of above-mentioned A component is: under nitrogen protection, with the small molecules polyether glycol and (or) plant oil modified polyvalent alcohol is heated to 130～150 ℃, under the vacuum tightness 0.266KPa, moisture content is surveyed in sampling behind dehydration 1.5～2h, when 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 the described B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; The acid anhydrides that is used 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: the small molecules polyether glycol is heated to 150～170 ℃, under the vacuum tightness 0.266KPa, water-content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, under 120～130 ℃, carry out sour modification, add again solidifying agent, obtain carboxylic polyether glycol.
The content of carboxyl is 4%～12% in the carboxylic polyether glycol of above-mentioned B component.
The preparation method of described solvent-free dual-component polyurethane adhesive is: under 15～20 ℃ of temperature, A component and B component are fully mixed by the mol ratio NCO/OH=1.0 of functional group～1.5.
Below be described in further detail technical scheme of the present invention as follows:
A kind of normal temperature coating no-solvent polyurethane composite gum comprises two components of A, B, it is characterized in that the A component is isocyanate terminated based polyurethanes performed polymer, and the B component is carboxylic polyether glycol; A component and B component are pressed the mol ratio NCO/OH=1.0 of functional group～1.5, preferred NCO/OH=1.3～1.5.
The raw material weight proportioning for preparing no-solvent polyurethane composite gum of the present invention is:
The A component: isocyanic ester 50%～75%,
Small molecules polyether glycol 15%～30%,
Plant oil modified polyvalent alcohol 10%～20%,
The 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 the B component gross weight 0.1%～0.3%.
Preferably, the raw material weight proportioning for preparing no-solvent polyurethane composite gum of the present invention is:
The A component: isocyanic ester 60%～75%,
Small molecules polyether glycol 15%～25%,
Plant oil modified polyvalent alcohol 10%～15%,
The 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 the B component gross weight 0.1%～0.3%.
Isocyanic ester in the A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); The 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 that 1000 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900 castor oil modified trivalent alcohol.
Small molecules polyether glycol in the B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; The acid anhydrides that is used for modification is trimellitic acid 1,2-anhydride; Solidifying agent is that 2-ethyl-4 Methylimidazole, glyoxal ethyline, butyl-glyoxal ethyline mix in the ratio of 2:1:1.
Through a large amount of experimental studies, when the content of carboxyl in the B component is controlled at 4%～12%, be surprisingly found out that, the compound fastness of no-solvent polyurethane composite gum of the present invention significantly strengthens, and has effectively eliminated the detrimentally affect that causes crawling to spare even can't be coated with because viscosity is too high after A, B component mix.Be the impact of different carboxyl-contents in the proof B component on the compound fastness of composite gum (this test adopts peeling force to measure compound fastness) and viscosity, the contriver has carried out following contrast experiment, and test-results sees Table one.Wherein sample 1 is the prepared composite gum of embodiment 11, and sample 2,3,4,5,6,7,8 preparation method are guaranteeing under the constant prerequisite of other raw materials and reaction conditions with reference to the method for embodiment 11, 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.
Carboxyl-content is on the impact of compound fastness and viscosity in table one, the B component
The testing data of table one shows, when the content of carboxyl in the B component less than 4% the time, solventless adhesive peeling force of the present invention is little, namely compound fastness is poor; When the content of carboxyl in the B component greater than 12% the time, the peeling force of solventless adhesive of the present invention is large, can satisfy composite demand, but the initial viscosity of joining behind the glue is excessive, is difficult to evenly be coated with at substrate surface.Hence one can see that, when the content of carboxyl in the B component 4%～12% the time, composite performance optimum and the modest viscosity of prepared solventless adhesive of the present invention are convenient to even coating.
The preparation method of above-mentioned solvent-free dual-component polyurethane composite gum may further comprise the steps:
(1) by the mol ratio NCO/OH=1.0 of functional group～1.5, take by weighing A, B component, each component takes by weighing raw material by following proportioning:
The A component: isocyanic ester 50%～75%,
Small molecules polyether glycol 15%～30%,
Plant oil modified polyvalent alcohol 10%～20%,
The 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 the B component gross weight 0.1%～0.3%.
(2) preparation A component: under the protection of nitrogen, small molecules polyether glycol and/or plant oil modified polyvalent alcohol are heated to 130～150 ℃, under the vacuum tightness 0.266KPa, moisture content is surveyed in sampling behind dehydration 1.5～2h, when 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) preparation B component: under the protection of nitrogen, the small molecules polyether glycol is heated to 150～170 ℃, under the vacuum tightness 0.266KPa, moisture content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, under 120～130 ℃, carry out sour modification, obtain carboxylic polyether glycol;
(4) solidifying agent of its raw material gross weight 0.1%～0.3% of adding in the B component;
(5) preparation composite gum: A component and B component in 15～20 ℃ of lower fully mixing of temperature, namely obtain the no-solvent polyurethane composite gum by the mol ratio NCO/OH of functional group=1.0～1.5.
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, have following beneficial effect among the present invention:
1. dual-component polyurethane composite gum of the present invention is difficult to the cementability that bonding base material shows excellence to some, such as bonded polyethylene (PE), polypropylene (CPP), aluminium foil etc., and made foil laminated film still keeps good cementability after 121 ℃ of boiling sterilizations are processed.
2. effectively eliminated A, the B component causes the detrimentally affect that crawling is even even can't be coated with because viscosity is too high after mixing, and prolongs composite gum working life.
3. significantly reduce solidification value, shorten set time.
4. solvent-free discharging in the 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 about 300m/min.
6. the unit surface glue consumption is little, saves cost.
Specific implementation method:
In order to further specify 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 the vacuum tightness 0.266KPa; water content is surveyed in sampling behind the dehydration 1.5h; when water-content ﹤ 0.05%, be cooled to 70 ℃, add 150 parts of HMDI, 125 parts of IPDI; at 85 ℃ of lower reaction 2h, obtain A component (hereinafter to be referred as A-1).
The preparation of embodiment 2:A-2
Under nitrogen protection; the polyoxytrimethylene triol of 120 parts of molecular weight 300, the soybean oil modified polyvalent alcohol of 80 parts of molecular weight 1000 (functionality 2.6) are heated to 150 ℃; under the vacuum tightness 0.266KPa; water content is surveyed in sampling behind the dehydration 2h; when water-content ﹤ 0.05%, be cooled to 70 ℃, add 150 parts of HMDI, 50 parts of IPDI; at 90 ℃ of lower reaction 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 the vacuum tightness 0.266KPa; water content is surveyed in sampling behind the dehydration 2h; when water-content ﹤ 0.05%, be cooled to 70 ℃, add 200 parts of HMDI, 100 parts of IPDI; at 90 ℃ of lower reaction 3h, obtain A component (hereinafter to be referred as A-2).
The preparation of embodiment 4:B-1
Under the protection of nitrogen; the polyoxytrimethylene triol of 40 parts of molecular weight 300, the polyoxypropyleneglycol of 9 parts of molecular weight 400 are joined in the reactor; be heated to 150 ℃ of vacuum hydro-extractions; water content is surveyed in sampling behind the dehydration 1.5h; when water-content ﹤ 0.05%, be cooled to 60 ℃, then add 1 part of trimellitic acid 1,2-anhydride; under 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 polyoxytrimethylene triol of 100 parts of molecular weight 300, the polyoxypropyleneglycol of 90 parts of molecular weight 400 are joined in the reactor; be heated to 170 ℃ of vacuum hydro-extractions; water content is surveyed in sampling behind the dehydration 2h, when water-content ﹤ 0.05%, is cooled to 60 ℃; add 10 parts of trimellitic acid 1,2-anhydrides; under 125 ℃, carry out sour modification, add again 0.1 part of 2-ethyl-4 Methylimidazole, 0.05 part of glyoxal ethyline, 0.05 part of butyl-glyoxal ethyline, obtain the B component.Hereinafter to be referred as B-3.
The preparation of embodiment 6:B-3
Under the protection of nitrogen; the polyoxytrimethylene triol of 100 parts of molecular weight 300, the polyoxypropyleneglycol of 50 parts of molecular weight 400 are joined in the reactor; be heated to 170 ℃ of vacuum hydro-extractions; water content is surveyed in sampling behind the dehydration 2h, when water-content ﹤ 0.05%, is cooled to 60 ℃; add 50 parts of trimellitic acid 1,2-anhydrides; under 130 ℃, carry out sour modification, add again 0.03 part of 2-ethyl-4 Methylimidazole, 0.015 part of glyoxal ethyline, 0.015 part of butyl-glyoxal ethyline, obtain the B component.Hereinafter to be referred as B-4.
Embodiment 7: take by weighing A-1, B-1 component by the mol ratio NCO/OH=1 of functional group, fully mix under 15 ℃, 20 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 8: take by weighing A-2, B-1 component by the mol ratio NCO/OH=1.2 of functional group, fully mix under 15 ℃, 20 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 9: take by weighing A-3, B-1 component by the mol ratio NCO/OH=1.3 of functional group, fully mix under 15 ℃, 20 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 10: take by weighing A-3, B-2 component by the mol ratio NCO/OH=1.4 of functional group, fully mix under 15 ℃, 20 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 11: take by weighing A-3, B-3 component by the mol ratio NCO/OH=1.5 of functional group, fully mix under 15 ℃, 20 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Table two, 15 ℃, 20 ℃ are joined glue after 2 minutes and the viscosity after 30 minutes
Embodiment 12: (embodiment 8-embodiment 11) prepares respectively two kinds of composite membranes with solvent-free dual-component polyurethane composite gum of the present invention: 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 under 15～20 ℃ and carry out, spread is 1.0g/m
2～2.0g/m
2, then after 48 hours, be cooled to room temperature 50 ℃ of lower slakings, composite membrane is cut into wide 15 millimeters, long 200 millimeters test bar is at room temperature measured T-shaped stripping strength with BLD-200 electron detachment trier, and draw speed is 100 in the least m/min.In addition, after 30 minutes, measure after the same method more T-shaped stripping strength respectively at 100 ℃, 121 ℃ poach, the results are shown in table three.In addition, above-mentioned composite membrane was observed more than 40 ℃ of lower 4 weeks of placement, composite membrane still keeps good appearance, pears skin, colloid flavescence phenomenon all do not occur.
The splitting power of table three, mensuration composite membrane
Comparative Examples 1: embodiment 7 and embodiment 8,9 difference 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 can finding, the initial viscosity of embodiment 8,9 when 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, when the small molecules polyvalent alcohol cooperates plant oil modified polyvalent alcohol to use, significantly reduced the initial viscosity of solvent-free composite gum.
Comparative Examples 2: embodiment 9 and embodiment 10,11 difference are that the B component of embodiment 9 does not add solidifying agent, and all add the solidifying agent of different ratios among the embodiment 10,11 B component.By finding that relatively embodiment 9 joins glue at 15 ℃, 20 ℃ and still is in liquid state after 30 minutes, affects surface covered, need to improve solidification value; Solidified after 30 minutes and embodiment 10,11 joins glue at 15 ℃, learnt that thus the solidifying agent that is added into suitable proportion has greatly reduced solidification value.
Claims (7)
1. a normal temperature is coated with solvent-free polyurethane adhesive, it is characterized in that, described solvent-free dual-component polyurethane adhesive comprises two components of A, B, and the A component is the isocyanate terminated based polyurethanes performed polymer that the plant oil modified polyol reaction by the small molecules polyether glycol of 50%～75% isocyanic ester and 15%～30% and/or 10%～20% generates; The B component is the carboxylic polyether glycol that the anhydride reaction by 75%～98% micromolecular polyether glycol and 2%～25% generates, solidifying agent account for other raw materials in the 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 the A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); The 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 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900 castor oil modified trivalent alcohol (functionality is 2.7).
3. normal temperature as claimed in claim 1 or 2 is coated with solvent-free polyurethane adhesive; 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 the vacuum tightness 0.266KPa; moisture content is surveyed in sampling behind dehydration 1.5～2h; when 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 the B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; The acid anhydrides that is used for modification is trimellitic acid 1,2-anhydride; Solidifying agent is 2-ethyl-4-methylimidazole.
5. such as claim 1 or 4 described normal temperature coating solvent-free polyurethane adhesives, it is characterized in that, the preparation method of the carboxylic polyether glycol of B component is: the small molecules polyether glycol is heated to 150～170 ℃, and under the vacuum tightness 0.266KPa, water-content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, under 120～130 ℃, carry out sour modification, add again solidifying agent, obtain carboxylic polyether glycol.
6. such as claim 1 or 4 described normal temperature coating solvent-free polyurethane adhesives, it is characterized in that the content of carboxyl is 4%～12% in the carboxylic polyether glycol of B component.
7. such as each described normal temperature coating solvent-free polyurethane adhesive of claim 1～7, it is characterized in that, the preparation method of normal temperature coating solvent-free polyurethane adhesive is: under 15～20 ℃ of temperature, A component and B component are fully mixed by the mol ratio NCO/OH=1.0 of functional group～1.5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103555429A (en) * | 2013-11-05 | 2014-02-05 | 湖北大学 | Preparation method of carboxylic hydrogenated castor oil polyalcohol |
| CN104449538A (en) * | 2014-12-04 | 2015-03-25 | 上海康达化工新材料股份有限公司 | Double-component solvent-free polyurethane structural adhesive coated at normal temperature, as well as preparation method and application method thereof |
| 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 |
| CN107814902A (en) * | 2017-11-06 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of polyurethane aqueous dispersion body of hydroxyl and its production and use |
| CN108559440A (en) * | 2018-04-27 | 2018-09-21 | 上海回天新材料有限公司 | A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging |
| WO2019128520A1 (en) * | 2017-12-29 | 2019-07-04 | 三星聚合物有限公司 | Solvent-free resin and preparation method therefor, preparation kit and use thereof |
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| WO2006011256A1 (en) * | 2004-07-30 | 2006-02-02 | Mitsui Chemicals Polyurethanes, Inc. | Two-component curable solventless adhesive |
| CN101280167A (en) * | 2007-04-02 | 2008-10-08 | 上海康达化工有限公司 | Solvent-free polyurethane laminating adhesive for normal temperature coating, preparation and use thereof |
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| WO2006011256A1 (en) * | 2004-07-30 | 2006-02-02 | Mitsui Chemicals Polyurethanes, Inc. | Two-component curable solventless adhesive |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555429A (en) * | 2013-11-05 | 2014-02-05 | 湖北大学 | Preparation method of carboxylic hydrogenated castor oil polyalcohol |
| CN103555429B (en) * | 2013-11-05 | 2016-01-20 | 湖北大学 | A kind of preparation method of carboxylic hydrogenated castor oil polyalcohol |
| CN104449538A (en) * | 2014-12-04 | 2015-03-25 | 上海康达化工新材料股份有限公司 | Double-component solvent-free polyurethane structural adhesive coated at normal temperature, as well as preparation method and application method thereof |
| 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 |
| CN107814902A (en) * | 2017-11-06 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of polyurethane aqueous dispersion body of hydroxyl and its production and use |
| WO2019128520A1 (en) * | 2017-12-29 | 2019-07-04 | 三星聚合物有限公司 | Solvent-free resin and preparation method therefor, preparation kit and use thereof |
| CN108559440A (en) * | 2018-04-27 | 2018-09-21 | 上海回天新材料有限公司 | A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging |
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