CN104211890B - A kind of aqueous polyurethane hydrophilic chain extender and preparation method thereof - Google Patents
A kind of aqueous polyurethane hydrophilic chain extender and preparation method thereof Download PDFInfo
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- CN104211890B CN104211890B CN201410441699.5A CN201410441699A CN104211890B CN 104211890 B CN104211890 B CN 104211890B CN 201410441699 A CN201410441699 A CN 201410441699A CN 104211890 B CN104211890 B CN 104211890B
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- chain extender
- aqueous polyurethane
- hydrophilic chain
- secondary amine
- solution
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 74
- 239000004814 polyurethane Substances 0.000 title claims abstract description 74
- 239000004970 Chain extender Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 45
- HUHXLHLWASNVDB-UHFFFAOYSA-N 2-(oxan-2-yloxy)oxane Chemical class O1CCCCC1OC1OCCCC1 HUHXLHLWASNVDB-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005562 Glyphosate Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940097068 glyphosate Drugs 0.000 claims abstract description 24
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 15
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 15
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940094989 trimethylsilane Drugs 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- -1 chloride tertiary amine Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 17
- 150000003512 tertiary amines Chemical class 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 244000144992 flock Species 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 150000001261 hydroxy acids Chemical group 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 4
- 229940043276 diisopropanolamine Drugs 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical group C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000004880 oxines Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000005906 dihydroxylation reaction Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 0 *N(*)C(N(CC(O)=O)CP(O)(O)=O)=O Chemical compound *N(*)C(N(CC(O)=O)CP(O)(O)=O)=O 0.000 description 1
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
Classifications
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to the preparation method of a kind of aqueous polyurethane hydrophilic chain extender, comprise the following steps: secondary amine is mixed by (1) with dihydropyran, sulphuric acid two (trimethyl silane) ester, add the dichloromethane of excess, prepare secondary amine two (tetrahydropyranyl ethers) solution；(2) dichloromethane of triphosgene with excess is mixed, drip triethylamine, then instill secondary amine two (tetrahydropyranyl ethers) solution described in step (1)；(3) by molten for glyphosate and described N position chloride tertiary amine two (tetrahydropyranyl ethers) solution reaction；(4) in the solution that step (3) prepares, stannum phosphate is added.The preparation method of the aqueous polyurethane hydrophilic chain extender of the present invention has the advantage of low cost, environmental protection, and whole technological process is simple, easily promotes.
Description
Technical field
The present invention relates to chain extender technical field, particularly to a kind of aqueous polyurethane hydrophilic chain extender and system thereof
Preparation Method.
Background technology
Hydrophilic chain extender is a kind of critical materials preparing aqueous polyurethane, and it is molten that it is that aqueous polyurethane is different from
One of substitutive characteristics of dosage form polyurethane.Aqueous polyurethane is exactly based on the main chain of polyurethane introducing parent
Water base group, and then just achieve the stable dispersion in water.
Hydrophilic chain extender can be divided into cationic, anionic and nonionic 3 class.Anionic is hydrophilic
Group has carboxylate, sulfonate, sulfate and phosphonate groups.For carboxylic acid type and the hydrophilic expansion of sulfonic acid type
The applied research of chain agent is the most, and the carboxylic acid type anionic hydrophilic chain extender as common has bishydroxymethyl propanoic acid
And dimethylolpropionic acid, conventional sulfonic acid type anionic hydrophilic chain extender have ethylenediamine base ethyl sulfonic acid sodium, 1,2-third
Glycol-3-sodium sulfonate and 1,4-butanediol-2-sodium sulfonate.The structure of hydrophilic chain extender typically contains can be with Carbimide.
The hydroxyl of ester reaction and certain type of hydrophilic group.
Applied research for the aqueous chain extender of single hydrophilic group is more at present, for the expansion of double-hydrophilic group
The research of chain agent is less.Prior art has the aqueous of hydroxy-acid group and phosphate group the most simultaneously
Polyurethane hydrophilic chain extender.
Summary of the invention
The technical problem to be solved is: provides one to have end position hydroxyl, and has carboxylic acid simultaneously
Aqueous polyurethane hydrophilic chain extender of group and phosphate group double-hydrophilic group and preparation method thereof.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is:
A kind of aqueous polyurethane hydrophilic chain extender, the structural formula of described aqueous polyurethane hydrophilic chain extender is:
Wherein, R1、R2For alkyl.
Having the beneficial effects that of the aqueous polyurethane hydrophilic chain extender of the present invention: the aqueous polyurethane parent of the present invention
Water chain extender contains the end position hydroxyl that can react with isocyanates, has hydroxy-acid group and phosphate group simultaneously
Double-hydrophilic group, can improve the problem that carboxylic acid type hydrophilic chain extender hydrophilic is inadequate, with described hydrophilic chain extension
The water dispersible of aqueous polyurethane prepared by agent and automatic emulsifying performance are more preferable, and less consumption just can make preparation
Aqueous polyurethane emulsion is stable, the advantage not only with the aqueous polyurethane of carboxylic acid type, simultaneously phosphate group
Introducing can make the aqueous polyurethane of preparation have excellent adhesive attraction and anti-flammability.
Invention additionally discloses the preparation method of a kind of aqueous polyurethane hydrophilic chain extender, comprise the following steps:
(1) secondary amine is mixed with dihydropyran, sulphuric acid two (trimethyl silane) ester, add the dichloro of excess
Methane, reaction 15～20min at-5 DEG C～0 DEG C, prepared secondary amine two (tetrahydropyranyl ethers) solution, described two
Hydrogen pyrans is (2～4) with the mol ratio of secondary amine: 1, and the addition of described sulphuric acid two (trimethyl silane) ester is
The 0.1%～0.5% of dihydropyran quality, described secondary amine has two end position hydroxyls；
(2) dichloromethane of triphosgene with excess is mixed, after being cooled to-15 DEG C～-10 DEG C, drip 1～5g
Triethylamine, stirs, and then instills secondary amine two (tetrahydropyranyl ethers) solution described in step (1), rises
High-temperature, to 25 DEG C～30 DEG C, reacts 2～4h, and the tertiary amine two (tetrahydropyranyl ethers) preparing the chloride of N position is molten
Liquid, described secondary amine is 3:(1～2 with the mol ratio of triphosgene)；
(3) glyphosate is dissolved in NaOH solution or 10%～40% mass concentration of 10%-40% mass concentration
Triethylamine solution in, after stirring, under constant-pressure conditions, at 25 DEG C～30 DEG C, at the uniform velocity drip step
(2) tertiary amine two (tetrahydropyranyl ethers) solution of the chloride of N position described in, time for adding is 2～2.5h, continues
Continuous stirring reaction 4～5h, described glyphosate is (1～1.2) with the mol ratio of secondary amine: 1；
(4) in the solution that step (3) prepares, 1～1.5g stannum-phosphate is added, anti-under the conditions of 30～35 DEG C
Answer 2～2.5h, prepare aqueous polyurethane hydrophilic chain extender.
Having the beneficial effects that of the preparation method of the aqueous polyurethane hydrophilic chain extender of the present invention:
(1) secondary amine with two end position hydroxyls is first reacted with dihydropyran so that end position hydroxyl is protected
Get up, it is to avoid secondary amine, during carrying out chloride, because of the side reaction holding position hydroxyl to cause, produces many groups
The chloride product of point mixture, thus the problem separating difficulty caused；
(2) selecting glyphosate is raw material, and the advantage with low cost, the advantages of nontoxic raw materials of selection, to people's
Injure low, simultaneous reactions mild condition, it is substantially all and can complete at room temperature environment, the advantage with environmental protection；
(3) intermediate product produced in building-up process need not purification and can carry out next step reaction, whole
Technological process is simple, easily promotes；
(4) the aqueous polyurethane hydrophilic chain extender prepared contains the end position hydroxyl that can react with isocyanates,
There is the double-hydrophilic group of hydroxy-acid group and phosphate group simultaneously, carboxylic acid type hydrophilic chain extender can be improved hydrophilic
The problem that property is inadequate, the water dispersible of the aqueous polyurethane prepared with described hydrophilic chain extender and automatic emulsifying performance
More preferably, less consumption just can make the aqueous polyurethane emulsion of preparation stablize, and not only has the aqueous of carboxylic acid type
The advantage of polyurethane, the introducing of phosphate group simultaneously can make the aqueous polyurethane of preparation have excellent adhesive attraction and
Anti-flammability.
Accompanying drawing explanation
Fig. 1 is the reaction scheme figure of the preparation method of the aqueous polyurethane hydrophilic chain extender of the embodiment of the present invention one；
Fig. 2 is the reaction scheme figure of the preparation method of the aqueous polyurethane hydrophilic chain extender of the embodiment of the present invention one.
Detailed description of the invention
By describing the technology contents of the present invention in detail, being realized purpose and effect, give below in conjunction with embodiment
With explanation.
The design of most critical of the present invention is: first the secondary amine with two end position hydroxyls is carried out hydroxyl protection again
Carry out the formylation reaction of secondary amine, then react with glyphosate, to prepare, there is end position hydroxyl and simultaneously
There is hydroxy-acid group and the aqueous polyurethane hydrophilic chain extender of phosphate group double-hydrophilic group.
The present invention provides a kind of aqueous polyurethane hydrophilic chain extender, the knot of described aqueous polyurethane hydrophilic chain extender
Structure formula is:
Wherein, R1、R2For alkyl.
Knowable to foregoing description, having the beneficial effects that of the aqueous polyurethane hydrophilic chain extender of the present invention: this
Bright aqueous polyurethane hydrophilic chain extender contains the end position hydroxyl that can react with isocyanates, has carboxylic acid simultaneously
The double-hydrophilic group of group and phosphate group, can improve the problem that carboxylic acid type hydrophilic chain extender hydrophilic is inadequate,
The water dispersible of the aqueous polyurethane prepared with described hydrophilic chain extender and automatic emulsifying performance are more preferable, less use
Amount just can make the aqueous polyurethane emulsion of preparation stablize, the advantage not only with the aqueous polyurethane of carboxylic acid type,
The introducing of phosphate group simultaneously can make the aqueous polyurethane of preparation have excellent adhesive attraction and anti-flammability.
The preparation method of a kind of aqueous polyurethane hydrophilic chain extender of the present invention, comprises the following steps:
(1) secondary amine is mixed with dihydropyran, sulphuric acid two (trimethyl silane) ester, add the dichloro of excess
Methane, reaction 15～20min at-5 DEG C～0 DEG C, prepared secondary amine two (tetrahydropyranyl ethers) solution, described two
Hydrogen pyrans is (2～4) with the mol ratio of secondary amine: 1, and the addition of described sulphuric acid two (trimethyl silane) ester is
The 0.1%～0.5% of dihydropyran quality, described secondary amine has two end position hydroxyls；
(2) dichloromethane of triphosgene with excess is mixed, after being cooled to-15 DEG C～-10 DEG C, drip 1～5g
Triethylamine, stirs, and then instills secondary amine two (tetrahydropyranyl ethers) solution described in step (1), rises
High-temperature, to 25 DEG C～30 DEG C, reacts 2～4h, and the tertiary amine two (tetrahydropyranyl ethers) preparing the chloride of N position is molten
Liquid, described secondary amine is 3:(1～2 with the mol ratio of triphosgene)；
(3) glyphosate is dissolved in NaOH solution or 10%～40% mass concentration of 10%-40% mass concentration
Triethylamine solution in, after stirring, under constant-pressure conditions, at 25 DEG C～30 DEG C, at the uniform velocity drip step
(2) tertiary amine two (tetrahydropyranyl ethers) solution of the chloride of N position described in, time for adding is 2～2.5h, continues
Continuous stirring reaction 4～5h, described glyphosate is (1～1.2) with the mol ratio of secondary amine: 1；
(4) in the solution that step (3) prepares, 1～1.5g stannum-phosphate is added, anti-under the conditions of 30～35 DEG C
Answer 2～2.5h, prepare aqueous polyurethane hydrophilic chain extender.
Knowable to foregoing description, the beneficial effect of the preparation method of the aqueous polyurethane hydrophilic chain extender of the present invention
It is:
(1) secondary amine with two end position hydroxyls is first reacted with dihydropyran so that end position hydroxyl is protected
Get up, it is to avoid secondary amine, during carrying out chloride, because of the side reaction holding position hydroxyl to cause, produces many groups
The chloride product of point mixture, thus the problem separating difficulty caused；
(2) selecting glyphosate is raw material, and the advantage with low cost, the advantages of nontoxic raw materials of selection, to people's
Injure low, simultaneous reactions mild condition, it is substantially all and can complete at room temperature environment, the advantage with environmental protection；
(3) intermediate product produced in building-up process need not purification and can carry out next step reaction, whole
Technological process is simple, easily promotes；
(4) the aqueous polyurethane hydrophilic chain extender prepared contains the end position hydroxyl that can react with isocyanates,
There is the double-hydrophilic group of hydroxy-acid group and phosphate group simultaneously, carboxylic acid type hydrophilic chain extender can be improved hydrophilic
The problem that property is inadequate, the water dispersible of the aqueous polyurethane prepared with described hydrophilic chain extender and automatic emulsifying performance
More preferably, less consumption just can make the aqueous polyurethane emulsion of preparation stablize, and not only has the aqueous of carboxylic acid type
The advantage of polyurethane, the introducing of phosphate group simultaneously can make the aqueous polyurethane of preparation have excellent adhesive attraction and
Anti-flammability.
Further, described step (3) is carried out under nitrogen protection.
Seen from the above description, under the protection of nitrogen, the anti-of the secondary amine after formylated and glyphosate can be made
Should stablize, interference-free is carried out.
Further, described dihydropyran, triphosgene, glyphosate are 6:1:3:3 with the mol ratio of secondary amine.
Seen from the above description, the mol ratio of the dihydropyran of the present embodiment, triphosgene, glyphosate and secondary amine
For preferred proportioning, there is reaction advantage abundant, efficient.
Further, step (5) is also included: what regulating step (4) prepared comprises described aqueous polyurethane parent
The pH value of the mixed liquor of water chain extender is less than or equal to 0, then carries out distillation process, precipitated sodium chloride；
Obtaining filtrate after filtration, the pH value of regulation filtrate is 4.0～5.0, and described filtrate carries out alcohol analysis process, separates out
White flock material, the most described aqueous polyurethane hydrophilic chain extender.
Seen from the above description, the preparation method of the aqueous polyurethane hydrophilic chain extender of the present embodiment is to prepared
The mixed liquor comprising described aqueous polyurethane hydrophilic chain extender carries out separating-purifying, thus water described in isolated
Property polyurethane hydrophilic chain extender.
Further, the analysis of described alcohol is processed as: described filtrate instilled in dehydrated alcohol.
Further, described aqueous polyurethane hydrophilic chain extender step (5) obtained is at 80 DEG C～100 DEG C
It is dried 20～24h, is dried process.
Seen from the above description, the preparation method of the aqueous polyurethane hydrophilic chain extender of the present embodiment is to step (5)
The described aqueous polyurethane hydrophilic chain extender obtained is dried process, convenient storage.
Embodiments of the invention one are:
1, step (1): the protection of end position hydroxyl
Take diethanolamine 100g and add in 500mL there-necked flask, add 170g dihydropyran, add 0.4g
Sulphuric acid two (trimethyl silane) ester, adds 50mL dichloromethane, reacts 18min, prepare second at 0 DEG C
Glycol amine two (tetrahydropyranyl ethers), standby.
2, step (2): the formylated of ethylene glycol amine two (tetrahydropyranyl ethers)
Addition 100g triphosgene and 50mL dichloromethane in another there-necked flask being dried, stirring and dissolving,
Triethylamine it is slowly added dropwise after being cooled to-15 DEG C.At-15 DEG C, above-mentioned solution is added drop-wise in triphosgene solution, drips
Add complete, be warmed to room temperature reaction 3 hours, obtain N-acyl chlorides-N, N-diethanol tertiary amine two (tetrahydropyranyl ethers).
3, step (3): react with glyphosate
Being dissolved in the sodium hydroxide solution of 10% mass fraction by 170g glyphosate, stirring is allowed to fully dissolve,
Pour four-hole boiling flask into.In constant pressure funnel load step (2) obtain solution of acid chloride, under nitrogen protection,
At ambient temperature, being added drop-wise to four-hole boiling flask, 2h dropping is complete, continues reaction 4h.
4, step (4): dehydroxylation protection and the purification of product
After step (3) completes, add 1g catalyst stannum-phosphate, under 35 DEG C of backflows, react 2h.Reaction
Liquid dense HCl regulation pH value to 0 or less, then distills with vacuum rotary evaporator, precipitated sodium chloride.
Filtrate again with NaOH solution regulation pH value to about 4.0, be added drop-wise in dehydrated alcohol, separate out white flock
Material.Product is dried 24h under vacuum drying oven, obtains white powder and is described hydrophilic chain extender.
The reaction scheme figure of the present embodiment refers to Fig. 1.
Embodiments of the invention two are:
1, step (1): the protection of end position hydroxyl
Take diisopropanolamine (DIPA) 133g and add in 500mL there-necked flask, add 170g dihydropyran, add 0.4g
Sulphuric acid two (trimethyl silane) ester, adds 50mL dichloromethane, reacts 18min, prepare two at 0 DEG C
Isopropanolamine two (tetrahydropyranyl ethers), standby.
2, step (2): the formylated of diisopropanolamine (DIPA) two (tetrahydropyranyl ethers)
Addition 100g triphosgene and 50mL dichloromethane in another there-necked flask being dried, stirring and dissolving,
3g triethylamine it is slowly added dropwise after being cooled to-15 DEG C.At-15 DEG C, above-mentioned solution is added drop-wise in triphosgene solution,
Drip complete, be warmed to room temperature reaction 3 hours, obtain N-acyl chlorides-N, N-diisopropanol tertiary amine two (Pentamethylene oxide.
Ether).
3, step (3): react with glyphosate
Being dissolved in the triethylamine solution of 10% mass fraction by 170g glyphosate, stirring is allowed to fully dissolve, and falls
Enter four-hole boiling flask.In constant pressure funnel load step (2) obtain solution of acid chloride, under nitrogen protection,
At ambient temperature, being added drop-wise to four-hole boiling flask, 2h dropping is complete, continues reaction 4h.
4, step (4): dehydroxylation protection and the purification of product
After step (3) completes, add 1g catalyst stannum-phosphate, under 35 DEG C of backflows, react 2h.Reaction
Liquid dense HCl regulation pH value to 0 or less, then distills with vacuum rotary evaporator, precipitated sodium chloride.
Filtrate again with NaOH solution regulation pH value to about 4.0, be added drop-wise in dehydrated alcohol, separate out white flock
Material.Product is dried 24h under vacuum drying oven, obtains white powder and is described hydrophilic chain extender.
The reaction scheme figure of the present embodiment refers to Fig. 2.
Embodiment three:
Step (1): mixed with dihydropyran, sulphuric acid two (trimethyl silane) ester by secondary amine, adds excess
Dichloromethane, at-5 DEG C react 15min, prepare secondary amine two (tetrahydropyranyl ethers) solution, described dihydro
Pyrans is 2:1 with the mol ratio of secondary amine, and the addition of described sulphuric acid two (trimethyl silane) ester is dihydro pyrrole
The 0.1% of quality of muttering, described secondary amine has two end position hydroxyls；
Step (2): mixed by the dichloromethane of triphosgene with excess, after being cooled to-15 DEG C, drips 1g tri-second
Amine, stirs, and then instills secondary amine two (tetrahydropyranyl ethers) solution described in step (1), rises high temperature
Degree, to 25 DEG C, reacts 2h, prepares tertiary amine two (tetrahydropyranyl ethers) solution of N position chloride, described secondary amine
It is 3:1 with the mol ratio of triphosgene；
Step (3): glyphosate is dissolved in the NaOH solution or the three of 10% mass concentration of 10% mass concentration
In ethylamine solution, after stirring, under constant-pressure conditions, at 25 DEG C, at the uniform velocity drip institute in step (2)
Stating tertiary amine two (tetrahydropyranyl ethers) solution of N position chloride, time for adding is 2h, continues stirring reaction 4h,
Described glyphosate is 1:1 with the mol ratio of secondary amine；
Step (4): add 1g stannum-phosphate in the solution that step (3) prepares, react under the conditions of 30 DEG C
2h, prepares aqueous polyurethane hydrophilic chain extender.
Embodiment four
Step (1): mixed with dihydropyran, sulphuric acid two (trimethyl silane) ester by secondary amine, adds excess
Dichloromethane, at 0 DEG C react 20min, prepare secondary amine two (tetrahydropyranyl ethers) solution, described dihydro
Pyrans is 4:1 with the mol ratio of secondary amine, and the addition of described sulphuric acid two (trimethyl silane) ester is dihydro pyrrole
The 0.5% of quality of muttering, described secondary amine has two end position hydroxyls；
Step (2): mixed by the dichloromethane of triphosgene with excess, after being cooled to-10 DEG C, drips 5g tri-second
Amine, stirs, and then instills secondary amine two (tetrahydropyranyl ethers) solution described in step (1), rises high temperature
Degree, to 30 DEG C, reacts 4h, prepares tertiary amine two (tetrahydropyranyl ethers) solution of N position chloride, described secondary amine
It is 3:2 with the mol ratio of triphosgene；
Step (3): glyphosate is dissolved in the NaOH solution or the three of 40% mass concentration of 40% mass concentration
In ethylamine solution, after stirring, under constant-pressure conditions, at 30 DEG C, at the uniform velocity drip institute in step (2)
Stating tertiary amine two (tetrahydropyranyl ethers) solution of N position chloride, time for adding is 2.5h, continues stirring reaction
5h, described glyphosate is 1.2:1 with the mol ratio of secondary amine；
Step (4): add 1.5g stannum-phosphate in the solution that step (3) prepares, anti-under the conditions of 35 DEG C
Answer 2.5h, prepare aqueous polyurethane hydrophilic chain extender.
Embodiment five:
Step (1): mixed with dihydropyran, sulphuric acid two (trimethyl silane) ester by secondary amine, adds excess
Dichloromethane, at-3 DEG C react 18min, prepare secondary amine two (tetrahydropyranyl ethers) solution, described dihydro
Pyrans is 3:1 with the mol ratio of secondary amine, and the addition of described sulphuric acid two (trimethyl silane) ester is dihydro pyrrole
The 0.3% of quality of muttering, described secondary amine has two end position hydroxyls；
Step (2): mixed by the dichloromethane of triphosgene with excess, after being cooled to-13 DEG C, drips 3g tri-second
Amine, stirs, and then instills secondary amine two (tetrahydropyranyl ethers) solution described in step (1), rises high temperature
Degree, to 27 DEG C, reacts 3h, prepares tertiary amine two (tetrahydropyranyl ethers) solution of N position chloride, described secondary amine
It is 3:1.5 with the mol ratio of triphosgene；
Step (3): glyphosate is dissolved in the NaOH solution or the three of 25% mass concentration of 25% mass concentration
In ethylamine solution, after stirring, under constant-pressure conditions, at 27 DEG C, at the uniform velocity drip institute in step (2)
Stating tertiary amine two (tetrahydropyranyl ethers) solution of N position chloride, time for adding is 2.3h, continues stirring reaction
4.5h, described glyphosate is 1.1:1 with the mol ratio of secondary amine；
Step (4): add 1.3g stannum-phosphate in the solution that step (3) prepares, anti-under the conditions of 33 DEG C
Answer 2.3h, prepare aqueous polyurethane hydrophilic chain extender.
In sum, the preparation method of the aqueous polyurethane hydrophilic chain extender that the present invention provides can avoid secondary amine
During carrying out chloride, because of the problem of the side reaction that end position hydroxyl causes；There is low cost, to people
Injury low, the advantage of environmental protection；Whole technological process is simple, easily promotes；The aqueous polyurethane parent prepared
Water chain extender can improve the problem that carboxylic acid type hydrophilic chain extender hydrophilic is inadequate, not only has the water of carboxylic acid type
The advantage of property polyurethane, the introducing of phosphate group simultaneously can make the aqueous polyurethane of preparation have excellent adhesive attraction
And anti-flammability.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every profit
The equivalents made by description of the invention content, or directly or indirectly it is used in relevant technical field,
The most in like manner it is included in the scope of patent protection of the present invention.
Claims (7)
1. an aqueous polyurethane hydrophilic chain extender, it is characterised in that described aqueous polyurethane hydrophilic chain extender
Structural formula be:
Wherein, R1、R2For alkyl.
2. the preparation method of an aqueous polyurethane hydrophilic chain extender, it is characterised in that comprise the following steps:
(1) secondary amine is mixed with dihydropyran, sulphuric acid two (trimethyl silane) ester, add the dichloro of excess
Methane, reaction 15～20min at-5 DEG C～0 DEG C, prepared secondary amine two (tetrahydropyranyl ethers) solution, described two
Hydrogen pyrans is (2～4) with the mol ratio of secondary amine: 1, and the addition of described sulphuric acid two (trimethyl silane) ester is
The 0.1%～0.5% of dihydropyran, described secondary amine has two end position hydroxyls；
(2) dichloromethane of triphosgene with excess is mixed, after being cooled to-15 DEG C～-10 DEG C, drip 1～5g
Triethylamine, stirs, and then instills secondary amine two (tetrahydropyranyl ethers) solution described in step (1), rises
High-temperature, to 25 DEG C～30 DEG C, reacts 2～4h, and the tertiary amine two (tetrahydropyranyl ethers) preparing the chloride of N position is molten
Liquid, described secondary amine is 3:(1～2 with the mol ratio of triphosgene)；
(3) glyphosate is dissolved in NaOH solution or the 10%-40% mass concentration of 10%-40% mass concentration
Triethylamine solution in, after stirring, under constant-pressure conditions, at 25 DEG C～30 DEG C, at the uniform velocity drip step
(2) tertiary amine two (tetrahydropyranyl ethers) solution of the chloride of N position described in, time for adding is 2～2.5h, continues
Continuous stirring reaction 4～5h, described glyphosate is (1-1.2) with the mol ratio of secondary amine: 1；
(4) in the solution that step (3) prepares, 1～1.5g stannum-phosphate is added, anti-under the conditions of 30～35 DEG C
Answer 2～2.5h, prepare aqueous polyurethane hydrophilic chain extender.
The preparation method of aqueous polyurethane hydrophilic chain extender the most according to claim 2, it is characterised in that
Described step (3) is carried out under nitrogen protection.
The preparation method of aqueous polyurethane hydrophilic chain extender the most according to claim 2, it is characterised in that
Described dihydropyran, triphosgene, glyphosate are 6:1:3:3 with the mol ratio of secondary amine.
The preparation method of aqueous polyurethane hydrophilic chain extender the most according to claim 2, it is characterised in that
Also include step (5): the mixing comprising described aqueous polyurethane hydrophilic chain extender that regulating step (4) prepares
The pH value of liquid is less than or equal to 0, then carries out distillation process, precipitated sodium chloride；Filtrate is obtained after filtration,
The pH value of regulation filtrate is 4.0～5.0, and described filtrate carries out alcohol analysis process, separates out white flock material,
The most described aqueous polyurethane hydrophilic chain extender.
The preparation method of aqueous polyurethane hydrophilic chain extender the most according to claim 5, it is characterised in that
The analysis of described alcohol is processed as: described filtrate instilled in dehydrated alcohol.
The preparation method of aqueous polyurethane hydrophilic chain extender the most according to claim 5, it is characterised in that
Described aqueous polyurethane hydrophilic chain extender step (5) obtained is dried 20～24h at 80 DEG C～100 DEG C,
It is dried process.
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| CN101935329A (en) * | 2010-08-20 | 2011-01-05 | 杨彦威 | Phosphate with dihydroxyl structure and preparation method thereof |
| CN103214668A (en) * | 2013-05-09 | 2013-07-24 | 东华大学 | Preparation method of chain extender for waterborne polyurethane |
| CN103524693A (en) * | 2013-10-28 | 2014-01-22 | 洋紫荆油墨(中山)有限公司 | Preparation method for aqueous polyurethane |
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| CN101935329A (en) * | 2010-08-20 | 2011-01-05 | 杨彦威 | Phosphate with dihydroxyl structure and preparation method thereof |
| CN103214668A (en) * | 2013-05-09 | 2013-07-24 | 东华大学 | Preparation method of chain extender for waterborne polyurethane |
| CN103524693A (en) * | 2013-10-28 | 2014-01-22 | 洋紫荆油墨(中山)有限公司 | Preparation method for aqueous polyurethane |
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