CN104774317B - A kind of preparation method of side chain alkyl polyurethane chain extender and products thereof - Google Patents
A kind of preparation method of side chain alkyl polyurethane chain extender and products thereof Download PDFInfo
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- CN104774317B CN104774317B CN201510162219.6A CN201510162219A CN104774317B CN 104774317 B CN104774317 B CN 104774317B CN 201510162219 A CN201510162219 A CN 201510162219A CN 104774317 B CN104774317 B CN 104774317B
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Abstract
The present invention relates to a kind of preparation method of side chain alkyl polyurethane chain extender and products thereof.The preparation method comprises the following steps：Raw material prepares：Diisocyanate, higher aliphatic, polyol, catalyst, organic solvent；Polyol dehydration pretreatment；Diisocyanate is alkylated；Side chain alkyl polyurethane chain extender is made in polyol alkylation.Preparation method of the present invention it is handling strong, equipment is simple.The side chain alkyl polyurethane chain extender prepared using this method can be used for the preparation of various polyurethane materials, to introduce the side chain alkyl of high level into polyurethane high molecule, assigns the obvious water repellent antifouling property of polyurethane material, has good market prospects；Product safety environmental protection, it is easy to use.
Description
Technical field
The present invention relates to the preparation for various polyurethane high molecule materials, with the introducing side long-chain into polyurethane high molecule
A kind of chain extender of alkyl, and in particular to preparation method of side chain alkyl polyurethane chain extender and products thereof.
Background technology
Polyurethane high molecule material is commonly used for the coating of all kinds of base materials and covered with paint, lacquer, colour wash, etc. to process.Covered with paint, lacquer, colour wash, etc. to solve conventional urethane
The problem of agent low temperature fatiguability and elasticity, extensibility, feature difference, through the monomer modified polyurethane finishing agent of various functions just
Have become the main product for covering with paint, lacquer, colour wash, etc. manufacture field.Functional urethane finishing agent is generally by block copolymerization, grafting and envelope
Various functions monomer or reactive functional molecular are introduced polyurethane skeleton and obtained by the chemical reaction such as end.It is however, existing
Various functions monomer is mostly monofuntional molecule structure, it is difficult to facilitated and accessed in large quantities among polyurethane high molecule,
Therefore modified effect is undesirable.Meanwhile current functional monomer lacks waterproofing function, it is difficult to obtain the poly- of waterproof and hydrolysis
Urethane material.
The functional urethane chain extender of functional urethane preparation is presently used for including following several：
1st, the preparation method of fluorine-containing diamine chain extender and high-strength, high-elastic high temperature resistant polyurethane, it is different that its raw material includes two
Cyanate, PTMEG, feature chain extender, diluent.
" fluorine-containing diamine is the synthesis of the polyurethane elastomer of chain extender as written by Kong Fanjia, Yang Xiaohui, Yao Hongxi et al.
And characterize " (《Polyurethane industrial》The 1st phases of volume 23 in 2008) disclose the preparation of fluorine-containing diamine chain extender and fluorochemical urethane
Method, in its raw material：Diisocyanate is toluene di-isocyanate(TDI), PTMEG is PolyTHF that molecular weight is 1000
Glycol, feature chain extender are using perfluor bisphenol-A as double [4- (4- amino-benzene oxygens) phenyl] hexafluoros third of the homemade 2,2- of raw material
Alkane, diluent are N,N-dimethylformamide.
The fluorine-containing diamine chain extender that this method obtains effectively can introduce fluorine-containing side chain to polyurethane high molecule, using its as
Fluorochemical urethane prepared by chain extender is due to the strong hydrogen bonding effect between hard section and dipole effect so that moiety segments arrange in microcell
Microstructure is formed in order, therefore with preferable heat-resisting and oxidation resistent susceptibility, the tensile strength and extension of material
Preferably.However, the preparation process of fluorine-containing diamine chain extender is extremely complex, yield is relatively low, cost is higher, in addition, using it as expansion
The cold resistance of fluorochemical urethane prepared by chain agent is also poor.
2nd, siliceous mixed chain extender and low-modulus polyurethane method for producing elastomers, its raw material include two isocyanic acids
Ester, hydrocarbon hydroxyl polysiloxane, feature chain extender, catalyst, diluent.
" organosilicon/chain expansion of succinic acid agent mixing ratio is gathered to mixing big glycol-based as written by Wang Yunfang, Guo Zengchang, Wang Rumin
The performance impact of urethane elastomer " (《Chinese adhesive》The 5th phases of volume 17 in 2008) disclosed in siliceous mixed chain extender and low mould
Weight polyurethane method for producing elastomers, in its raw material：Diisocyanate is 4,4- methyl diphenylene diisocyanates, hydrocarbon hydroxyl
Based polysiloxane is the α that homemade hydroxyl value is 12.07mgKOH/g, ω-bis- (γ-hydroxypropyl) dimethyl silicone polymers and hydroxyl value
It is double (4- hydroxyls the butyl) -1,1,3,3- tetramethyls two of 1,3- for 160mgKOH/g polyoxy tetramethylene, feature chain extender
The mixture of siloxanes and 1,4- butanediols, catalyst are stannous octoate, diluent is dimethylformamide and tetrahydrofuran
Mixture.
The siliceous mixed chain extender that this method is prepared can obviously improve the flexibility of polyurethane elastomer, but to the pole of material
Limiting tensile strength influences less.Except this, heat resistance is poor.Meanwhile polyurethane high molecule material prepared by this method is in the absence of bright
True cross-linked structure, the microphase separation degree of the high polymer material is higher in addition, therefore water resistance is poor.
3rd, the mixed chain extender of the side base of pyrimidone containing urea and the preparation method of flexible urethane elastomer, its raw material include
Diisocyanate, PTMEG, feature chain extender, catalyst, diluent.
" synthesis of Quadrupolar hydrogen bond chain extender and its shadow to polyurethane performance as written by Feng Zhicheng, Zhu Bo, Shi Jinjun et al.
Ring " (《Polyurethane industrial》The 2nd phases of volume 26 in 2011) the disclosed side base of pyrimidone containing urea mixed chain extender and flexible polyurethane
Method for producing elastomers, in its raw material：Diisocyanate is hexamethylene diisocyanate, PTMEG is that molecular weight is
1400 polytetrahydrofuran diol, feature chain extender are homemade [1H]-pyrimidine ketone group-l, 3- third of two ureas of 2- methyl -2-2- 4
The mixture of glycol and 1,4- butanediols, catalyst are dibutyl tin dilaurate, diluent is dimethylformamide.
The mixed chain extender for the side base of pyrimidone containing urea that this method is prepared can obviously improve polyurethane elastomer flexibility,
Extension and tensile strength, and high molecular main chain is not easy thermal cracking.However, the polyurethane prepared with the mixed chain extender
The initial decomposition temperature of elastomer is relatively low.Meanwhile the preparation process of the chain extender of the side base of pyrimidone containing urea is extremely complex, yield compared with
It is low, cost is higher, using its as chain extender prepare polyurethane elastomer cold resistance it is also poor.
The content of the invention
The technical problems to be solved by the invention are：There is provided a kind of side chain alkyl polyurethane chain extender preparation method and
Its product.The chain extender can be used for the side chain alkyl that high level is introduced into polyurethane high molecule, assign polyurethane material
The performance that obvious water repellent is antifouling and low temperature is soft, has good market prospects.
The present invention is that technical scheme is used by solving above-mentioned technical problem：
The preparation method of side chain alkyl polyurethane chain extender, it is characterised in that：Comprise the following steps：
(1) raw material prepares：Diisocyanate, higher aliphatic, polyol, catalyst, organic solvent, by mole
Fraction meter, diisocyanate 1, higher aliphatic 1, polyol 1；
(2) the step of polyol dehydration pretreatment, the step is by polyol under vacuum, heating condition
Dehydration pretreatment is carried out, anhydrous polyol is made；
(3) diisocyanate be alkylated the step of, the step by diisocyanate, higher aliphatic catalyst catalysis
Under reacted, be made alkylation diisocyanate；
(4) the step of polyol is alkylated, the step will be alkylated diisocyanate and anhydrous polyhydroxy chemical combination
Thing is reacted in presence of organic solvent, and alkylation polyol, i.e. side chain alkyl polyurethane chain extender is made.
By such scheme, the temperature of step (2) vacuum dehydration is 90~100 DEG C, vacuum -0.100~-0.098MPa,
40~80min of dewatering time.
By such scheme, step (3) reaction temperature is 70~90 DEG C, 80~120min of reaction time.
By such scheme, step (4) reaction temperature is 50~70 DEG C, reacts 70~100min.
By such scheme, the diisocyanate is toluene di-isocyanate(TDI), IPDI, 1,6- two
One kind in isocyanates.
By such scheme, described higher aliphatic is a length of 8~12 (C of carbon8~C12) saturated monohydroxy alcohol in one kind.
By such scheme, polyol is one kind in the trihydroxylic alcohol that molecular weight is 90~150 or ternary hydramine.
By such scheme, the catalyst is stannous octoate or dibutyl tin laurate, and the quality of catalyst is different for two
The 0.02~0.05% of cyanate, higher aliphatic and polyol three's gross weight.
By such scheme, the organic solvent of the step (4) is one in acetone, MEK, ethyl acetate, butyl acetate
Kind, the dosage of organic solvent is to be normally carried out course of reaction.
By such scheme, the preparation method of above-mentioned side chain alkyl polyurethane chain extender specifically includes following steps：
(1) requirement in such scheme prepares raw material；
(2) polyol is put into dehydration device；90~100 DEG C are heated to, in the true of -0.100~-0.098MPa
40~80min is handled under reciprocal of duty cycle；Less than 50 DEG C are cooled to, vacuum is released, is sealed, anhydrous polyol is made；
(3) diisocyanate is put into reaction unit, is warming up to 50~70 DEG C, higher aliphatic is added dropwise in 30~60min
Alcohol simultaneously controls temperature as 50~70 DEG C, then adds catalyst, and controlling reaction temperature is 70~90 DEG C, reacts 80~120min,
Alkylation diisocyanate is made；
(4) above-mentioned reaction system is cooled to 50~70 DEG C；Anhydrous polyol is put into reaction system, is maintained
It is 50~70 DEG C to stir and control temperature, reacts 70~100min, during which adds organic solvent in right amount several times, to control reaction
The viscosity of system, alkylation polyol, i.e. side chain alkyl polyurethane chain extender is made.
According to side chain alkyl polyurethane chain extender made from the preparation method of above-mentioned side chain alkyl polyurethane chain extender
Product.
Compared with prior art, the inventive method has advantages below and feature：
1st, the present invention passes through two isocyanic acids using the high selectivity and high activity reacted between isocyanate groups and hydroxyl
Higher aliphatic is connected by ester with multifunctional hydroxy compounds, obtains the polyurethane chain extender containing side chain alkyl.Preparation side
Method is handling strong, and technical process is simple, with short production cycle, and production equipment is easy to get without particular/special requirement, required raw material.
2nd, the present invention has efficiently controlled the structure of product by the design and control to reactant ratio, feeding sequence,
Product structure is clear and definite, accessory substance is few, yield is high, and the side chain alkyl polyurethane chain extender of preparation is in water white transparency viscous fluid
Body, safety and environmental protection are easy to use.
3rd, side chain alkyl polyurethane chain extender prepared by the present invention can be conveniently and in large quantities to various anion, cation
And chain alkyl side chain is introduced in non-ionic polyurethane macromolecular scaffold, course of reaction is steady, easily-controllable；Prepared using it as chain extender
Polyurethane high molecule material there is low temperature soft, deep drawing quality and the good characteristics such as significant water repellent is antifouling.
Embodiment
The preparation method of the chain alkyl polyurethane chain extender in side of the present invention of embodiment 1
The raw material of the preparation method includes：
Diisocyanate：Toluene di-isocyanate(TDI) 1mol (174.2g)
Higher aliphatic：N-octyl alcohol 1mol (130.2g)
Polyol：Glycerine 1mol (92.1g)
Catalyst：Stannous octoate 0.12g
Organic solvent：Acetone 40g
The specific steps of the preparation method：
(1) the step of polyol dehydration pretreatment, the step is by polyol under vacuum, heating condition
Dehydration pretreatment is carried out, anhydrous polyol is made；Specially：
(1.1) polyol is put into dehydration device；
(1.2) 95~100 DEG C are heated to, 60min is handled under -0.099MPa vacuum；
(1.3) less than 50 DEG C are cooled to, vacuum is released, is sealed, anhydrous polyol is made.
(2) diisocyanate be alkylated the step of, the step by diisocyanate, higher aliphatic catalyst catalysis
Under reacted, be made alkylation diisocyanate；Specially：
(2.1) diisocyanate is put into reaction unit,
55~60 DEG C are warming up to, it is 55~60 DEG C that higher aliphatic is added dropwise in 40min and controls temperature；
(2.2) catalyst is added into the reaction system of step (2.1), controlling reaction temperature is 75~80 DEG C, reaction
100min, alkylation diisocyanate is made.
(3) the step of polyol is alkylated, the step will be alkylated diisocyanate and anhydrous polyhydroxy chemical combination
Thing is reacted, and alkylation polyol, i.e. side chain alkyl polyurethane chain extender is made.Specially：
(3.1) reaction system of step (2.2) is cooled to 50~55 DEG C；
(3.2) put into anhydrous polyol into the reaction system of (3.1), maintain to stir and control temperature for 55~
60 DEG C, 80min is reacted, during which adds organic solvent in right amount several times, to control the viscosity of reaction system, alkylation polyhydroxy is made
Based compound, i.e. side chain alkyl polyurethane chain extender.
Product purpose usage prepared by the inventive method：The inventive method prepare side chain alkyl polyurethane chain extender be in
Water white transparency thick liquid, available for the side chain alkyl that high level is introduced into various polyurethane high molecules, and itself and mesh
Preceding various conventional non-ionic polyurethane chain extenders are compared, the water repellent that can significantly improve polyurethane material is antifouling, low temperature is soft and
Anti- tortuous performance, the imparting obvious water repellent of polyurethane material is antifouling, the soft and anti-tortuous performance of low temperature.
Product storage prepared by the inventive method：Finished product must be sealed at shady and cool, drying.
The preparation method of the chain alkyl polyurethane chain extender in side of the present invention of embodiment 2
The raw material of the preparation method includes：
Diisocyanate：Isoflurane chalcone diisocyanate 1mol (222.3g)
Higher aliphatic：Decanol 1mol (158.3g)
Polyol：Butantriol 1mol (106.1g)
Catalyst：Dibutyl tin laurate 0.20g
Organic solvent：MEK 50g
The specific steps of the preparation method：
(1) the step of polyol dehydration pretreatment, the step is by polyol under vacuum, heating condition
Dehydration pretreatment is carried out, anhydrous polyol is made；Specially：
(1.1) polyol is put into dehydration device；
(1.2) 100 DEG C are heated to, 80min is handled under -0.098MPa vacuum；
(1.3) less than 50 DEG C are cooled to, vacuum is released, is sealed, anhydrous polyol is made.
(2) diisocyanate be alkylated the step of, the step by diisocyanate, higher aliphatic catalyst catalysis
Under the conditions of reacted, be made alkylation diisocyanate；Specially：
(2.1) diisocyanate is put into reaction unit,
60~65 DEG C are warming up to, it is 60~65 DEG C that higher aliphatic is added dropwise in 30min and controls temperature；
(2.2) catalyst is added into the reaction system of step (2.1), controlling reaction temperature is 80 ± 2 DEG C, reaction
110min, alkylation diisocyanate is made.
(3) the step of polyol is alkylated, the step will be alkylated diisocyanate and anhydrous polyhydroxy chemical combination
Thing is reacted, and alkylation polyol, i.e. side chain alkyl polyurethane chain extender is made.Specially：
(3.1) reaction system of step (2.2) is cooled to 55~60 DEG C；
(3.2) put into anhydrous polyol into the reaction system of (3.1), maintain to stir and control temperature for 65~
70 DEG C, 90min is reacted, during which adds organic solvent in right amount several times, to control the viscosity of reaction system, alkylation polyhydroxy is made
Based compound, i.e. side chain alkyl polyurethane chain extender.
Product purpose usage prepared by the inventive method：The inventive method prepare side chain alkyl polyurethane chain extender be in
Water white transparency thick liquid, available for the side chain alkyl that high level is introduced into various polyurethane high molecules.Its with it is current
Various conventional non-ionic polyurethane chain extenders are compared, and the water repellent that can significantly improve polyurethane material is antifouling, low temperature is soft and anti-
Tortuous performance, the imparting obvious water repellent of polyurethane material is antifouling, the soft and anti-tortuous performance of low temperature.
Product storage prepared by the inventive method：Finished product must be sealed at shady and cool, drying.
The preparation method of the chain alkyl polyurethane chain extender in side of the present invention of embodiment 3
The raw material of the preparation method includes：
Diisocyanate：Hexamethylene diisocyanate 1mol (168.0g)
Higher aliphatic：Lauryl alcohol 1mol (186.3g)
Polyol：Triethanolamine 1mol (149.2g)
Catalyst：Stannous octoate 0.19g
Organic solvent：Butyl acetate 60g
The specific steps of the preparation method：
(1) the step of polyol dehydration pretreatment, the step is by polyol under vacuum, heating condition
Dehydration pretreatment is carried out, anhydrous polyol is made；Specially：
(1.1) polyol is put into dehydration device；
(1.2) 100 DEG C are heated to, 70min is handled under -0.099MPa vacuum；
(1.3) less than 50 DEG C are cooled to, vacuum is released, is sealed, anhydrous polyol is made.
(2) diisocyanate be alkylated the step of, the step by diisocyanate, higher aliphatic catalyst catalysis
Under reacted, be made alkylation diisocyanate；Specially：
(2.1) diisocyanate is put into reaction unit,
65~70 DEG C are warming up to, it is 65~70 DEG C that higher aliphatic is added dropwise in 40min and controls temperature；
(2.2) catalyst is added into the reaction system of step (2.1), controlling reaction temperature is 85 ± 2 DEG C, reaction
120min, alkylation diisocyanate is made.
(3) the step of polyol is alkylated, the step will be alkylated diisocyanate and anhydrous polyhydroxy chemical combination
Thing is reacted, and alkylation polyol, i.e. side chain alkyl polyurethane chain extender is made.Specially：
(3.1) reaction system of step (2.2) is cooled to 50~55 DEG C；
(3.2) put into anhydrous polyol into the reaction system of (3.1), maintain to stir and control temperature for 50~
55 DEG C, 70min is reacted, during which adds organic solvent in right amount several times, to control the viscosity of reaction system, alkylation polyhydroxy is made
Based compound, i.e. side chain alkyl polyurethane chain extender.
Product purpose usage prepared by the inventive method：The inventive method prepare side chain alkyl polyurethane chain extender be in
Water white transparency thick liquid, available for the side chain alkyl that high level is introduced into various polyurethane high molecules.Its with it is current
Various conventional non-ionic polyurethane chain extenders are compared, and the water repellent that can significantly improve polyurethane material is antifouling, low temperature is soft and anti-
Tortuous performance, the imparting obvious water repellent of polyurethane material is antifouling, the soft and anti-tortuous performance of low temperature.
Product storage prepared by the inventive method：Finished product must be sealed at shady and cool, drying.
It the foregoing is only the preferred embodiments of the present invention, actually each specific raw material cited by the present invention, and each original
Bound, the section value of material, and bound, the section value of technological parameter (such as temperature, time) can realize this hair
It is bright, embodiment numerous to list herein.
Therefore, above example is not intended to limit the invention, and those skilled in the art is in technical solution of the present invention model
Enclosing the usual variations and alternatives of interior progress should all include within the scope of the present invention.
Claims (8)
1. the preparation method of side chain alkyl polyurethane chain extender, it is characterised in that：Comprise the following steps：
（1）Raw material prepares：Diisocyanate, higher aliphatic, polyol, catalyst, organic solvent, by molar fraction
Meter, diisocyanate 1, higher aliphatic 1, polyol 1；
（2）The step of polyol dehydration pretreatment, the step carries out polyol under vacuum, heating condition
Dehydration pretreatment, is made anhydrous polyol；
（3）The step of diisocyanate is alkylated, the step enters diisocyanate, higher aliphatic under the catalysis of catalyst
Row reaction, alkylation diisocyanate is made；
（4）The step of polyol is alkylated, the step will be alkylated diisocyanate and exist with anhydrous polyol
Reacted in the presence of organic solvent, alkylation polyol, i.e. side chain alkyl polyurethane chain extender is made；
Described higher aliphatic is one kind in the saturated monohydroxy alcohol of carbon a length of 8~12；
Polyol is one kind in the trihydroxylic alcohol that molecular weight is 90~150 or ternary hydramine.
2. the preparation method of chain alkyl polyurethane chain extender in side according to claim 1, it is characterised in that：Step（2）
The temperature of vacuum dehydration is 90~100 DEG C, vacuum -0.100~-0.098MPa, 40~80min of dewatering time.
3. the preparation method of chain alkyl polyurethane chain extender in side according to claim 1, it is characterised in that：Step（3）
Reaction temperature is 70~90 DEG C, 80~120min of reaction time.
4. the preparation method of chain alkyl polyurethane chain extender in side according to claim 1, it is characterised in that：Step（4）
Reaction temperature is 50~70 DEG C, reacts 70~100min.
5. the preparation method of chain alkyl polyurethane chain extender in side according to claim 1, it is characterised in that：Described two is different
Cyanate is one kind in toluene di-isocyanate(TDI), IPDI, 1,6- di-isocyanates.
6. the preparation method of chain alkyl polyurethane chain extender in side according to claim 1, it is characterised in that：The catalysis
Agent is stannous octoate or dibutyl tin laurate, and the quality of catalyst is diisocyanate, higher aliphatic and polyhydroxylated
The 0.02~0.05% of compound three's gross weight；
The step（4）Organic solvent be acetone, MEK, ethyl acetate, one kind in butyl acetate, the use of organic solvent
Measure to be normally carried out course of reaction.
7. the preparation method of chain alkyl polyurethane chain extender in side according to claim 1, it is characterised in that：It is specifically wrapped
Include following steps：
（1）Prepare raw material according to claim 1；
（2）Polyol is put into dehydration device；90~100 DEG C are heated to, in -0.100~-0.098MPa vacuum
40~80min of lower processing；Less than 50 DEG C are cooled to, vacuum is released, is sealed, anhydrous polyol is made；
（3）Diisocyanate is put into reaction unit, is warming up to 40~50 DEG C, 50~70 DEG C are continuously heating to, in 30~60min
Interior dropwise addition higher aliphatic simultaneously controls temperature as 50~70 DEG C, then adds catalyst, and controlling reaction temperature is 70~90 DEG C, instead
80~120min is answered, alkylation diisocyanate is made；
（4）Above-mentioned reaction system is cooled to 50~70 DEG C；Anhydrous polyol is put into reaction system, maintains stirring
And it is 50~70 DEG C to control temperature, reacts 70~100min, organic solvent is during which added in right amount several times, to control reaction system
Viscosity, alkylation polyol, i.e. side chain alkyl polyurethane chain extender is made.
8. side made from the preparation method of the side chain alkyl polyurethane chain extender according to any one of claim 1-7 is grown
Alkyl group polyurethane chain extender product.
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| CN108047419B (en) * | 2017-12-15 | 2020-05-22 | 淄博鲁瑞精细化工有限公司 | Preparation method of fluffy polyurethane modified organic silicon softening agent |
| CN114621416B (en) * | 2020-12-09 | 2023-08-11 | 万华化学集团股份有限公司 | Aqueous polyurethane dispersion, preparation method and application thereof in double-component spray adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687172A (en) * | 2005-04-06 | 2005-10-26 | 华南理工大学 | Method for preparing aqueous dispersoid of comb type polyurethane |
| CN102898612A (en) * | 2012-10-31 | 2013-01-30 | 丽水学院 | Preparation method of linear water-based polyurethane thickener containing hydrophobic side bases |
| CN103497308A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Low temperature high elastic type waterproof antifouling water-based polyurethane finishing agent preparing method and product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687172A (en) * | 2005-04-06 | 2005-10-26 | 华南理工大学 | Method for preparing aqueous dispersoid of comb type polyurethane |
| CN102898612A (en) * | 2012-10-31 | 2013-01-30 | 丽水学院 | Preparation method of linear water-based polyurethane thickener containing hydrophobic side bases |
| CN103497308A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Low temperature high elastic type waterproof antifouling water-based polyurethane finishing agent preparing method and product |
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