CN103848952B - A kind of synthetic method of organic silicon modified polyurethane prepolymer and application - Google Patents
A kind of synthetic method of organic silicon modified polyurethane prepolymer and application Download PDFInfo
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- CN103848952B CN103848952B CN201410081320.4A CN201410081320A CN103848952B CN 103848952 B CN103848952 B CN 103848952B CN 201410081320 A CN201410081320 A CN 201410081320A CN 103848952 B CN103848952 B CN 103848952B
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- modified polyurethane
- polyurethane prepolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to the material of a kind of monomer through preliminary polymerization, be specifically related to a kind of synthetic method and application of organic silicon modified polyurethane prepolymer.It is that successively (molecular weight is 4000 with polyether Glycols in use diphenylmethanediisocyanate (MDI100), the commercially available trade mark is D4000) and hydroxyl-containing silicone (get hydroxyl modification polydimethylsiloxane, the commercially available trade mark is BD-3253, molecular weight is 3000) carry out polyreaction, a organic-silicon-modified urethane end-NCO based prepolymers obtained.It solve the problem of the gluing relative salt spray corrosion resistance difference of urethane in prior art, thus realize the technical requirements of marine glue stick.
Description
Technical field
The present invention relates to the material of a kind of monomer through preliminary polymerization, be specifically related to a kind of synthetic method and application of organic silicon modified polyurethane prepolymer.
Background technology
Organosilicon has been used to the modification of urethane very early, have high temperature resistant because the Si-O-Si key in the middle of its molecular chain has larger internal cohesive energy, the performance that hydrolysis etc. are excellent, and this chain belongs to flexible chain, there is the advantages such as low-temperature flexibility is good, surface tension is low, good biocompatibility, with it, base polyurethane prepolymer for use as is carried out to the modification of physics or chemistry, the over-all properties of tackiness agent can be improved, especially improve the weathering resistance of tackiness agent and resistance to marine abrasion.Document shows, the research of organic silicon modified polyurethane is embodied in the end NCO base with silane moiety or whole end capped polyether or polyester mostly, to reach the effect improving bonding interface and reduce surface imperfection, performed polymer structural molecule main chain remains the segment of urethane, real realization does not introduce Si-O-Si key, in fact cannot reach the high durable of marine glue stick and resistance to marine abrasion requirement.
Summary of the invention
In order to solve the problem of the gluing relative salt spray corrosion resistance difference of urethane in prior art, the present invention is by with polyether Glycols, (molecular weight is 4000, the commercially available trade mark is D4000) and with the alkane hydroxyl polysiloxane (BD-3253 of active end group (-OH), molecular weight is 3000) carry out polyaddition reaction with '-diphenylmethane diisocyanate (MDI100) respectively, make organic block polyurethane prepolymer, thus realize the technical requirements of marine glue stick.
The technological line of synthesis is:
Concrete synthetic method, comprises following steps:
The first step, puts into there-necked flask by the hydroxyl-containing silicone of 1 times mole, vacuum hydro-extraction 2 ~ 3h at 120 ± 5 DEG C, and inflated with nitrogen of then lowering the temperature is placed for subsequent use;
Second step, puts into there-necked flask, vacuum hydro-extraction 2 ~ 3h at 120 ± 5 DEG C by the polyether Glycols of 8-10 times mole, then less than 60 DEG C are cooled to, gradation adds the diphenylmethanediisocyanate of 23.6 ~ 35.7 times moles, controls temperature of reaction 80 ± 5 DEG C, reaction 2h;
3rd step, less than 60 DEG C are cooled to after second step completes, start to drip the 1 times of mole of hydroxyl-containing silicone removing water in advance with dropping funnel, it is per second that rate of addition is that 1-2 drips, controlling temperature of reaction is 80 ± 5 DEG C, until after being added dropwise to complete, continues reaction 2h, after having reacted, obtain tackiness agent prepolymer.
Further, described hydroxyl-containing silicone is commercially available BD-3253, molecular weight 3000; The commercially available trade mark of described polyether Glycols is D4000, and molecular weight is 4000; The commercially available trade mark of described diphenylmethanediisocyanate is MDI-100.
The NCO content of the organic silicon modified polyurethane prepolymer that the reaction of above-mentioned synthetic method generates is 3-4%, and this organic silicon modified polyurethane prepolymer of aforesaid method synthesis can application in marine glue stick.
Compared with prior art, in prepolymer of the present invention, viscoelastic state is in use temperature district as the polysiloxane segment of soft section and polyether segment, and hard section such as carbamate groups, gland base are in vitreous state or crystal form, the existence of soft section makes material have good elasticity, hard section part makes the strength of materials increase as physical crosslinking point, thus uses prepolymer of the present invention to prepare polyurethane adhesive, has good salt spray corrosion resistance.
Embodiment
Embodiment 1:
Weighing 1800 grams of polyether Glycols D4000 puts in there-necked flask, and vacuum hydro-extraction 2 ~ 3h at 120 ± 5 DEG C, is then cooled to less than 60 DEG C, and gradation adds diphenylmethanediisocyanate MDI100400 gram, controls temperature of reaction 80 ± 5 DEG C, reaction 2h.After the time, cool to 50 DEG C, start to drip the hydroxyl-containing silicone BD-3253150 gram that previously prepd removed water, rate of addition be 2 per second, controlling temperature of reaction is 80 ± 5 DEG C, until after being added dropwise to complete, continues reaction 1 hour, after the time, cooling discharge, obtains tackiness agent prepolymer.
Embodiment 2:
Weighing 1600 grams of polyether Glycols D4000 puts in there-necked flask, and vacuum hydro-extraction 2 ~ 3h at 120 ± 5 DEG C, is then cooled to less than 60 DEG C, and gradation adds diphenylmethanediisocyanate MDI100360 gram, controls temperature of reaction 80 ± 5 DEG C, reaction 2h.After the time, cool to 50 DEG C, start to drip the hydroxyl-containing silicone BD-3253150 gram that previously prepd removed water, rate of addition be 2 per second, controlling temperature of reaction is 80 ± 5 DEG C, until after being added dropwise to complete, continues reaction 1 hour, after the time, cooling discharge, obtains tackiness agent prepolymer.
Embodiment 3:
Weighing 2000 grams of polyether Glycols D4000 puts in there-necked flask, and vacuum hydro-extraction 2 ~ 3h at 120 ± 5 DEG C, is then cooled to less than 60 DEG C, and gradation adds diphenylmethanediisocyanate MDI100440 gram, controls temperature of reaction 80 ± 5 DEG C, reaction 2h.After the time, cool to 50 DEG C, start to drip the hydroxyl-containing silicone BD-3253150 gram that previously prepd removed water, rate of addition be 2 per second, controlling temperature of reaction is 80 ± 5 DEG C, until after being added dropwise to complete, continues reaction 1 hour, after the time, cooling discharge, obtains tackiness agent prepolymer.
The Comparison study citing of prepolymer of the present invention in tackiness agent:
Get commercially available conventional polyether-MDI(without any modification) prepolymer (the commercially available trade mark is 6605E), the organic silicon modified polyurethane prepolymer obtained with the embodiment of the present invention 1 is appropriate, and NCO content is 3.65%.Press surface compositions and prepare polyurethane adhesive respectively.
First: 6605E prepolymer 500 grams, 200 grams, softening agent, calcium powder 200 grams, carbon black 200 grams, catalyzer is appropriate.
Second: prepolymer of the present invention 500 grams, 200 grams, softening agent, calcium powder 200 grams, carbon black 200 grams, catalyzer is appropriate.
The first and second two of preparation glue samples are made adhesive tape and carries out salt-fog test test, the test of salt mist experiment is according to GB GB/T2423.17-1993, and test data is in table one.
table one
From table viewed from data, employ conventional without modified prepolymers in first glue formula, after have passed through salt-fog test, intensity and unit elongation decline by a big margin, and residual stretch intensity does not almost have, and adhesive tape loses the due elasticity of polyurethane adhesive.And in second glue formula, employ the organic-silicon-modified prepolymer of the present invention, after the salt-fog test of 1000 hours, performance has almost no change.
Claims (2)
1. a synthetic method for organic silicon modified polyurethane prepolymer, comprises following steps:
The hydroxyl-containing silicone that 1 times of mole of trade mark is BD-3253 by the first step, molecular weight is 3000 puts into there-necked flask, vacuum hydro-extraction 2 ~ 3h at 120 ± 5 DEG C, and inflated with nitrogen of then lowering the temperature is placed for subsequent use;
Second step, be D4000 by 8 ~ 10 times of moles of trades mark, molecular weight be 4000 polyether Glycols put into there-necked flask, vacuum hydro-extraction 2 ~ 3h at 120 ± 5 DEG C, then less than 60 DEG C are cooled to, it is the diphenylmethanediisocyanate of MDI-100 that gradation adds 23.6 ~ 35.7 times of moles of trades mark, control temperature of reaction 80 ± 5 DEG C, reaction 2h;
3rd step, less than 60 DEG C are cooled to after second step completes, start to drip the hydroxyl-containing silicone removing water in advance with dropping funnel, it is per second that rate of addition is that 1-2 drips, and controlling temperature of reaction is 80 ± 5 DEG C, until after being added dropwise to complete, continue reaction 2h, after having reacted, obtain tackiness agent prepolymer, in prepolymer, NCO content is 3-4%.
2. the application of a kind of organic silicon modified polyurethane prepolymer in marine glue stick of claim 1 preparation.
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| CN201410081320.4A CN103848952B (en) | 2014-03-07 | 2014-03-07 | A kind of synthetic method of organic silicon modified polyurethane prepolymer and application |
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| CN103848952B true CN103848952B (en) | 2016-01-20 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221661A (en) * | 2016-08-31 | 2016-12-14 | 芜湖恒耀汽车零部件有限公司 | For the high-temperature resistance adhesive that automobile exhaust pipe is bonding |
| CN106281186A (en) * | 2016-08-31 | 2017-01-04 | 芜湖恒耀汽车零部件有限公司 | Preparation method for the bonding high-temperature resistance adhesive of automobile exhaust pipe |
| CN106750082A (en) * | 2016-12-27 | 2017-05-31 | 广州市斯洛柯高分子聚合物有限公司 | A kind of silicon-based polyurethane oligomer and preparation method thereof |
| CN107383375B (en) * | 2017-08-11 | 2021-03-30 | 烟台德邦科技股份有限公司 | Preparation method of organic silicon modified polyester for modifying TPU (thermoplastic polyurethane) |
| CN107987710B (en) * | 2017-11-15 | 2019-10-01 | 上海途灏实业有限公司 | A kind of preparation method of the polyurea waterproof coating material applied to concrete surface |
| CN110483726A (en) * | 2019-08-16 | 2019-11-22 | 无锡庄周新材料科技有限公司 | A kind of one-component polyurethane and preparation method |
| CN111019468B (en) * | 2019-12-26 | 2021-11-19 | 无锡达美新材料有限公司 | Organic silicon modified release agent and preparation method and application thereof |
| CN111978851A (en) * | 2020-08-31 | 2020-11-24 | 荆晓东 | High-temperature-resistant and water-resistant waterborne polyurethane coating and preparation method thereof |
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| CN101096585A (en) * | 2007-06-22 | 2008-01-02 | 中国科学院广州化学研究所 | Nano organic montmorillonite modified end-silicane-group organosilicon modified polyurethane type seal gum and preparation method thereof |
| CN101864165A (en) * | 2010-05-05 | 2010-10-20 | 陕西浩瀚新宇科技发展有限公司 | Organic-silicon-modified polyurethane sealant and processing technology thereof |
| CN102127199A (en) * | 2010-01-15 | 2011-07-20 | 周建明 | Diisocyanate prepolymer as curing agent and preparation method thereof |
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- 2014-03-07 CN CN201410081320.4A patent/CN103848952B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101096585A (en) * | 2007-06-22 | 2008-01-02 | 中国科学院广州化学研究所 | Nano organic montmorillonite modified end-silicane-group organosilicon modified polyurethane type seal gum and preparation method thereof |
| CN102127199A (en) * | 2010-01-15 | 2011-07-20 | 周建明 | Diisocyanate prepolymer as curing agent and preparation method thereof |
| CN101864165A (en) * | 2010-05-05 | 2010-10-20 | 陕西浩瀚新宇科技发展有限公司 | Organic-silicon-modified polyurethane sealant and processing technology thereof |
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| 有机硅改性硅烷化聚氨酯密封胶的研制;王文荣，刘伟区，苏倩倩;《化学建材》;20071231;第23卷(第 4期);1 实验部分，2 结果与讨论 * |
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