CN103992462A - Preparation method and application of polyurethane associative thickener - Google Patents
Preparation method and application of polyurethane associative thickener Download PDFInfo
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- CN103992462A CN103992462A CN201310051618.6A CN201310051618A CN103992462A CN 103992462 A CN103992462 A CN 103992462A CN 201310051618 A CN201310051618 A CN 201310051618A CN 103992462 A CN103992462 A CN 103992462A
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- Prior art keywords
- associative thickener
- polyurethane associative
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- reaction
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- 239000002562 thickening agent Substances 0.000 title claims abstract description 104
- 239000004814 polyurethane Substances 0.000 title claims abstract description 100
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003973 paint Substances 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 86
- 239000000463 material Substances 0.000 claims description 61
- 230000018044 dehydration Effects 0.000 claims description 39
- 238000006297 dehydration reaction Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 35
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010985 leather Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- 230000008719 thickening Effects 0.000 abstract description 25
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 12
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000008118 PEG 6000 Substances 0.000 description 9
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 125000005474 octanoate group Chemical group 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- UQWCOJYUCIGJMD-UHFFFAOYSA-N 3,4-diethyl-7-phenylheptan-1-ol Chemical compound C(C)C(CCO)C(CCCC1=CC=CC=C1)CC UQWCOJYUCIGJMD-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ROYKLBDMDIUQRZ-UHFFFAOYSA-N 3,4-diethyloctan-1-ol Chemical compound C(C)C(CCO)C(CCCC)CC ROYKLBDMDIUQRZ-UHFFFAOYSA-N 0.000 description 1
- TUDPHQWZSGAFND-UHFFFAOYSA-N CCCCCCCCC(CCCC1=CC=CC=C1)C(CCCCCCCC)CCO Chemical compound CCCCCCCCC(CCCC1=CC=CC=C1)C(CCCCCCCC)CCO TUDPHQWZSGAFND-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method and application of a polyurethane associative thickener, and belongs to the field of thickeners. The method comprises: at 50-150 DEG C, completely reacting a dehydrated dihydric alcohol and a diisocyanate under the effect of a catalyst, so as to obtain an intermediate; mixing the intermediate with an end-capping reagent according to a molar ratio of 1:2, reacting at 30-100 DEG C to obtain the polyurethane associative thickener. The end-capping reagent has the structural formula shown in the specification, and the in structural formula, R is an epoxy group, an alkyl or a phenyl ring, x is an integer of 0-10, y is an integer of 0-10, and z is an integer of 0-30. The structural characteristic of the end-capping reagent enables the thickening effect of the thickener to be stable, the viscosity variation of paint employing the thickener is not large when the environment temperature changes, so that the problem is avoided that the normal usage of the paint is influenced by relatively large viscosity variation of the paint caused by environment temperature variation.
Description
Technical field
The present invention relates to thickening material field, particularly aqueous polyurethane associative thickener of a kind of efficient stable and preparation method thereof.
Background technology
Thickening material is a kind of auxiliary agent that can improve melt viscosity or liquid viscosity.At the conventional thickening material of paint field, it is polyurethane associative thickener.In coating system, polyurethane associative thickener forms micella as molecules surfactant, connects water-wet side and hydrophobic end, forms tridimensional network in system, and system viscosity is increased, and has also improved the rheological property of coating system simultaneously.
In patent CN1840587A, with dodecanol, do end-capping reagent, synthesized polyurethane associative thickener.
In realizing process of the present invention, contriver finds that prior art at least exists following problem:
The thickener system muddiness that above-mentioned patent is synthetic, and viscosity is larger, is not easy to disperse in water-based system.Use the viscosity of the coating system of general thickening material to change along with extraneous temperature variation, the painting of winter preparation expects that summer may be too small and need to add thickening material due to viscosity again, and the painting of preparation in summer expects that may affect because viscosity is excessive application property winter again.
Summary of the invention
In order to solve the problem of prior art, the embodiment of the present invention provides a kind of preparation method and application of polyurethane associative thickener.Described technical scheme is as follows:
On the one hand, provide a kind of preparation method of polyurethane associative thickener, described method comprises:
At 50 ~ 150 ℃, make dibasic alcohol and vulcabond complete reaction under catalyst action of dehydration, obtain intermediate;
Described intermediate is mixed according to the ratio of mol ratio 1:2 with end-capping reagent, and at 30 ~ 100 ℃, reaction obtains polyurethane associative thickener, and wherein, the structural formula of described end-capping reagent is as follows:
In structural formula: R is epoxy group(ing), alkane or phenyl ring;
X is 0 ~ 10 integer;
Y is 0 ~ 10 integer;
Z is 0 ~ 30 integer.
Particularly, the dewatering of described dibasic alcohol specifically comprises:
Dibasic alcohol material is put into the reactor with prolong and thermometer, under vacuum state, at 80 ~ 120 ℃, dewater 2 ~ 4 hours, arrive material moisture lower than 0.5%.
Particularly, described at 50 ~ 150 ℃, make dehydration dibasic alcohol and vulcabond complete reaction under catalyst action, obtain intermediate, specifically comprise:
In reactor, add catalyzer, at 50 ℃ ~ 150 ℃, in the dibasic alcohol of dehydration, drip vulcabond while stirring, after dripping, react 1～24 hour, follow the tracks of NCO group in detection reaction system, when the quality percentage composition of NCO group is less than or equal to 1.2%, finish reaction, obtain intermediate.
Particularly, described at 30 ~ 100 ℃ reaction obtain polyurethane associative thickener, specifically comprise: at 30 ~ 100 ℃, react 2 ~ 12 hours, follow the tracks of NCO group in detection reaction system, when the quality percentage composition of NCO group is less than 0.05%, finish reaction, obtain polyurethane associative thickener.
Preferably, described dibasic alcohol is that molecular weight is 10000 ~ 50000 polyoxyethylene glycol.
Preferably, described vulcabond is isophorone diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or diphenylmethanediisocyanate.
Particularly, the mol ratio of described vulcabond and described dibasic alcohol is 1 ~ 2:1.
Preferably, described catalyzer is one or more combinations in stannous octoate, dibutyl tin laurate, dibutyl tin maleate, zinc octoate.
Particularly, the quality of used catalyst is 0.05 ~ 10% of vulcabond and dibasic alcohol total mass.
On the other hand, provide polyurethane associative thickener prepared by the aforesaid method application in emulsion paint, varnish, tackiness agent, leather, papermaking, printing and dyeing, ink, makeup and personal care articles.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
Polyurethane associative thickener thickening effectiveness provided by the invention is good.Simultaneously, the end-capping reagent that the present invention adopts has specific structure, the structural performance of this end-capping reagent makes this thickening material thickening effectiveness stable, use coating variation of viscosity when envrionment temperature changes of this thickening material little, avoided changing the normal problem of using of considerable influence coating because variation of ambient temperature causes dope viscosity.Coating is used thickening material provided by the invention to use without adjusting to fill a prescription can realize under the environment of differing temps.Polyurethane associative thickener provided by the invention is a kind of bright market prospects and superior thickening material of over-all properties of having.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below embodiment of the present invention is described further in detail.
The embodiment of the present invention is raw materials used is commercial product except end-capping reagent; The end-capping reagent of using in the embodiment of the present invention carries out Guerbet reaction with branched-chain alcoho, becomes the alcohol of higly branched chain, then uses alcohol and the reacting ethylene oxide of this higly branched chain, obtains the polyether structure of molecule second half section.
The embodiment of the present invention provides a kind of preparation method of polyurethane associative thickener, and described method comprises:
Step 1: at 50 ~ 150 ℃, make dibasic alcohol and vulcabond complete reaction under catalyst action of dehydration, obtain intermediate;
In embodiment provided by the invention, specifically to dibasic alcohol, dewater by the following method: dibasic alcohol material is put into the reactor with prolong and thermometer, under vacuum state, at 80 ~ 120 ℃, dewater 2 ~ 4 hours, arrive material moisture lower than 0.5%.Water content is used karl Fischer aquametry to measure.
In order to guarantee that dibasic alcohol fully contacts with vulcabond, complete reaction, the reactor that the embodiment of the present invention provides is with whipping appts, to dibasic alcohol, dewater in backward reactor and add catalyzer, temperature of reaction is adjusted at 50 ℃ ~ 150 ℃, stir the dibasic alcohol of dehydration, and in the dibasic alcohol of dehydration, drip vulcabond while stirring, after dripping, react 1～24 hour, in reaction process, follow the tracks of NCO group in detection reaction system, when the quality percentage composition of NCO group is less than or equal to 1.2%, finish reaction, obtain intermediate.The method that the embodiment of the present invention provides according to HG2409-1992-T is followed the tracks of the content that detects NCO group.
Step 2: described intermediate is mixed according to the ratio of mol ratio 1:2 with end-capping reagent, and reaction obtains polyurethane associative thickener at 30 ~ 100 ℃, and wherein, the structural formula of described end-capping reagent is as follows:
In structural formula: R is epoxy group(ing), alkane or phenyl ring;
X is 0 ~ 10 integer;
Y is 0 ~ 10 integer;
Z is 0 ~ 30 integer.
In order to guarantee intermediate and end-capping reagent complete reaction, make the product that obtains more single, in the embodiment of the present invention, this step specifically comprises: described intermediate is mixed according to the ratio of mol ratio 1:2 with end-capping reagent, at 30 ~ 100 ℃, react 2 ~ 12 hours, follow the tracks of NCO group in detection reaction system, when the quality percentage composition of NCO group is less than 0.05%, finish reaction, pour out the material in reactor, obtain polyurethane associative thickener.The method that the embodiment of the present invention provides by HG2409-1992-T is followed the tracks of the content that detects NCO group.
Polyurethane associative thickener provided by the invention is solid, is inconvenient to use, the mobility that become after dissolving, more convenient use.The embodiment of the present invention is dissolved in polyurethane associative thickener in appropriate amount of deionized water, makes 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
In the embodiment of the present invention:
The polyoxyethylene glycol (PEG) that described dibasic alcohol preferred molecular weight is 10000 ~ 50000;
The preferred isophorone diisocyanate IPDI of described vulcabond, dicyclohexyl methane diisocyanate HMDI, hexamethylene diisocyanate HDI, tolylene diisocyanate TDI or diphenylmethanediisocyanate MDI;
Preferably, the mol ratio of described vulcabond and described dibasic alcohol is 1 ~ 2:1;
One or more combinations in the sub-tin of described catalyzer preferably octanoic acid, dibutyl tin laurate, dibutyl tin maleate, zinc octoate;
The quality of used catalyst is 0.05 ~ 10% of vulcabond and dibasic alcohol total mass.Polyurethane associative thickener prepared by the method providing by the embodiment of the present invention can be applied in the fields such as emulsion paint, varnish, tackiness agent, leather, papermaking, printing and dyeing, ink, makeup and personal care articles.
Embodiment 1
Take raw material: take 120gPEG6000,6.66gIPDI, 0.063g dibutyl tin maleate and 9.61g end-capping reagent 1, wherein end-capping reagent 1 is 3,4-diethyl-1-octanol polyoxyethylene, ten ethers, and its structural formula is as follows:
Prepare polyurethane associative thickener: the PEG6000 of 120g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 80 ℃, dewater 4 hours, arrive material moisture lower than 0.1%.Catalyzer dibutyl tin maleate is joined in reactor, with whipping appts, stir the PEG6000 of dehydration, and in the PEG6000 of dehydration, drip IPDI while stirring, after 6.66gIPDI is dripped, at 80 ℃, react 12 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.9.61g end-capping reagent 1 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.04% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 2
Take raw material: take 80gPEG8000,3.490gTDI, 0.083g dibutyl tin laurate and 9.61g end-capping reagent 1.
Prepare polyurethane associative thickener: the PEG8000 of 80g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 2 hours, arrive material moisture lower than 0.5%.Catalyzer dibutyl tin laurate is joined in reactor, with whipping appts, stir the PEG8000 of dehydration, and in the PEG8000 of dehydration, drip TDI while stirring, after 3.490gTDI is dripped, at 80 ℃, react 12 hours, in reaction system, the quality percentage composition of NCO group is 0.7% after testing, finishes mid point reaction.9.61g end-capping reagent 1 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.03% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 3
Take raw material: take 100gPEG10000,4.45gIPDI, 0.1g stannous octoate and 11.18g end-capping reagent 2, wherein end-capping reagent 2 is 3,4-diethyl-7-phenyl-1-heptanol polyoxyethylene, 20 ethers, and its structural formula is as follows:
Prepare polyurethane associative thickener: the PEG10000 of 100g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 3 hours, arrive material moisture lower than 0.3%.The sub-tin of octoate catalyst is joined in reactor, with whipping appts, stir the PEG10000 of dehydration, and in the PEG10000 of dehydration, drip IPDI while stirring, after 4.45gIPDI is dripped, at 80 ℃, react 12 hours, in reaction system, the quality percentage composition of NCO group is 0.8% after testing, finishes mid point reaction.11.18g end-capping reagent 2 is added in reactor, be uniformly mixed, react 6 hours at 30 ℃, in reaction system, the quality percentage composition of NCO group is 0.04% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 4
Take raw material: take 200gPEG20000,3.26gHDI, 0.2g zinc octoate and 11.44g end-capping reagent 2.
Prepare polyurethane associative thickener: the PEG20000 of 200g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 120 ℃, dewater 4 hours, arrive material moisture lower than 0.1%.Octoate catalyst zinc is joined in reactor, with whipping appts, stir the PEG20000 of dehydration, and in the PEG20000 of dehydration, drip HDI while stirring, after 3.26gHDI is dripped, at 120 ℃, react 6 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.11.44g end-capping reagent 2 is added in reactor, be uniformly mixed, react 6 hours at 100 ℃, in reaction system, the quality percentage composition of NCO group is 0.04% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 5
Take raw material: take 200gPEG20000,3.48gMDI, 10.17g dibutyl tin laurate and 9.62g end-capping reagent 1.
Prepare polyurethane associative thickener: the PEG20000 of 200g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 120 ℃, dewater 4 hours, arrive material moisture lower than 0.05%.Octoate catalyst zinc is joined in reactor, with whipping appts, stir the PEG20000 of dehydration, and in the PEG20000 of dehydration, drip HDI while stirring, after 3.48gMDI is dripped, at 100 ℃, react 1 hour, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.9.62g end-capping reagent 1 is added in reactor, be uniformly mixed, react 12 hours at 50 ℃, in reaction system, the quality percentage composition of NCO group is 0.04% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 6
Take raw material: take 180gPEG6000,8.88gIPDI, 0.76g stannous octoate and 11.44g end-capping reagent 2.
Prepare polyurethane associative thickener: the PEG6000 of 180g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 4 hours, arrive material moisture lower than 0.3%.The sub-tin of octoate catalyst is joined in reactor, with whipping appts, stir the PEG6000 of dehydration, and in the PEG6000 of dehydration, drip IPDI while stirring, after 8.88gIPDI is dripped, at 50 ℃, react 12 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.11.44g end-capping reagent 2 is added in reactor, be uniformly mixed, react 2 hours at 100 ℃, in reaction system, the quality percentage composition of NCO group is 0.02% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 7
Take raw material: take 200gPEG10000,10gHMDI, 0.63g dibutyl tin maleate and 11.44g end-capping reagent 2.
Prepare polyurethane associative thickener: the PEG10000 of 180g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 4 hours, arrive material moisture lower than 0.1%.Catalyzer dibutyl tin maleate is joined in reactor, with whipping appts, stir the PEG10000 of dehydration, and in the PEG10000 of dehydration, drip HMDI while stirring, after 8.88gHMDI is dripped, at 80 ℃, react 12 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.11.44g end-capping reagent 2 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.01% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 8
Take raw material: take 400gPEG20000,5.52gTDI, 0.63g stannous octoate and 11.44g end-capping reagent 2.
Prepare polyurethane associative thickener: the PEG20000 of 400g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 120 ℃, dewater 4 hours, arrive material moisture lower than 0.15%.The sub-tin of octoate catalyst is joined in reactor, with whipping appts, stir the PEG20000 of dehydration, and in the PEG20000 of dehydration, drip TDI while stirring, after 5.52gTDI is dripped, at 150 ℃, react 1 hour, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.11.44g end-capping reagent 2 is added in reactor, be uniformly mixed, react 6 hours at 100 ℃, in reaction system, the quality percentage composition of NCO group is 0.01% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 9
Take raw material: take 500gPEG10000,10.08gTDI, 1.02g dibutyl tin laurate and 11.44g end-capping reagent 2.
Prepare polyurethane associative thickener: the PEG10000 of 500g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 4 hours, arrive material moisture lower than 0.05%.Catalyzer dibutyl tin laurate is joined in reactor, with whipping appts, stir the PEG10000 of dehydration, and in the PEG10000 of dehydration, drip TDI while stirring, after 10.08gTDI is dripped, at 120 ℃, react 4 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.11.44g end-capping reagent 2 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.01% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 10
Take raw material: take 300gPEG10000,10.00gHMDI, 31g dibutyl tin maleate and 16.22g end-capping reagent 3, wherein end-capping reagent 3 is 3,4-dioctyl-7-phenyl-1-heptanol polyoxyethylene, 20 ethers, and its structural formula is as follows:
Prepare polyurethane associative thickener: the PEG10000 of 300g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 4 hours, arrive material moisture lower than 0.1%.Catalyzer dibutyl tin maleate is joined in reactor, with whipping appts, stir the PEG10000 of dehydration, and in the PEG10000 of dehydration, drip HMDI while stirring, after 10.00gHMDI is dripped, at 100 ℃, react 2 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.16.22g end-capping reagent 3 is added in reactor, be uniformly mixed, react 3 hours at 100 ℃, in reaction system, the quality percentage composition of NCO group is 0.01% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 11
Take raw material: take 240gPEG8000,10.00gMDI, 0.25g stannous octoate and 16.22g end-capping reagent 3.
Prepare polyurethane associative thickener: the PEG8000 of 300g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 4 hours, arrive material moisture lower than 0.05%.The sub-tin of octoate catalyst is joined in reactor, with whipping appts, stir the PEG8000 of dehydration, and in the PEG8000 of dehydration, drip MDI while stirring, after 10.00gMDI is dripped, at 80 ℃, react 12 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.16.22g end-capping reagent 3 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.03% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 12
Take raw material: take 480gPEG8000,14.48g IPDI, 0.99g zinc octoate and 11.44g end-capping reagent 2.
Prepare polyurethane associative thickener: the PEG8000 of 480g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 2 hours, arrive material moisture lower than 0.2%.Octoate catalyst zinc is joined in reactor, with whipping appts, stir the PEG8000 of dehydration, and in the PEG8000 of dehydration, drip IPDI while stirring, after 14.48g IPDI is dripped, at 140 ℃, react 8 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.11.44g end-capping reagent 2 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.03% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 13
Take raw material: take 400gPEG20000,6.66g IPDI, 0.81g stannous octoate and 11.44g end-capping reagent 2.
Prepare polyurethane associative thickener: the PEG20000 of 400g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 100 ℃, dewater 4 hours, arrive material moisture lower than 0.2%.The sub-tin of octoate catalyst is joined in reactor, with whipping appts, stir the PEG20000 of dehydration, and in the PEG20000 of dehydration, drip IPDI while stirring, after 6.66g IPDI is dripped, at 150 ℃, react 4 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.11.44g end-capping reagent 2 is added in reactor, be uniformly mixed, react 3 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.04% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 14
Take raw material: take 300gPEG6000,15.00gHMDI, 1.58g dibutyl tin laurate and 5.12g end-capping reagent 4, wherein unit alcohol 4 is 3,4-diethyl-7-phenyl-1-heptanol, and its structural formula is as follows:
Prepare polyurethane associative thickener: the PEG6000 of 400g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 120 ℃, dewater 4 hours, arrive material moisture lower than 0.2%.Catalyzer dibutyl tin laurate is joined in reactor, with whipping appts, stir the PEG6000 of dehydration, and in the PEG6000 of dehydration, drip HMDI while stirring, after 15.00gHMDI is dripped, at 50 ℃, react 12 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.5.12g end-capping reagent 4 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.03% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
Embodiment 15
Take raw material: take 320gPEG8000,15.00gHMDI, 2.35g zinc octoate and 5.12g unit alcohol 4.
Prepare polyurethane associative thickener: the PEG8000 of 320g is put into the reactor with prolong, thermometer and whipping appts, under vacuum state, at 120 ℃, dewater 2 hours, arrive material moisture lower than 0.05%.Octoate catalyst zinc is joined in reactor, with whipping appts, stir the PEG8000 of dehydration, and in the PEG8000 of dehydration, drip HMDI while stirring, after 15.00gHMDI is dripped, at 100 ℃, react 5 hours, in reaction system, the quality percentage composition of NCO group is 0.6% after testing, finishes mid point reaction.5.12g end-capping reagent 4 is added in reactor, be uniformly mixed, react 6 hours at 80 ℃, in reaction system, the quality percentage composition of NCO group is 0.03% after testing, finishes reaction, pours out while hot the material in reactor, obtains polyurethane associative thickener.
Take the above-mentioned polyurethane associative thickener of 30g, be dissolved in 70g deionized water, make 30%(mass percent) the aqueous polyurethane associative thickener that admittedly contains.
The aqueous polyurethane associative thickener that the embodiment of the present invention is provided and two kinds of commercially available thickening material products (thickening material RM2020, thickening material UH450) carry out application performance test:
Test condition: above-mentioned thickening material is applied in respectively in formulation for coating material and makes test sample, the viscosity of testing each sample differing temps with and temperature varying coefficient (viscosity/20 of 40 ℃ ℃ viscosity).
Formulation for coating material is as shown in table 1:
Table 1 formulation for coating material
In table 1: aqueous polyurethane associative thickener or two kinds of commercially available thickening materials that thickening material provides for embodiment of the present invention 1-15; Slurry is specifically filled a prescription in Table 2.
Table 2 coating formula of size
Testing method:
To under turn 600/min of each test sample, stir 15 minutes.Take out a standing evening, rotary viscosimeter instrument tested viscosity data for second day, test 20 ℃, and 30 ℃, the viscosity of 40 ℃ is also calculated variation factor (viscosity/20 of 40 ℃ ℃ viscosity).
Test result: in Table 3
Each temperature-viscosity of each test sample of table 3 and variation factor
By upper table 3, can find out that the thickening material that embodiment 1 ~ 15 provides compares with two kinds of commercially available thickening materials, the thickening material that embodiment 1 ~ 15 provides is very wide on range of viscosities, and substantially the variation factor of viscosity with temperature between 0.85-0.95, viscosity with temperature changes little, and RM2020 and UH450 are in temperature variation, viscosity alters a great deal, and variation factor is in 0.65 left and right.
As can be seen here, polyurethane associative thickener thickening effectiveness provided by the invention is good.Meanwhile, the end-capping reagent that the embodiment of the present invention adopts has specific structure, and this end-capping reagent belongs to water oil both sexes segment and is easy to be dissolved in water-based system, makes whole system totally limpid; Coating variation of viscosity when envrionment temperature changes of the thickening material that the use embodiment of the present invention provides is little, has avoided changing the normal problem of using of considerable influence coating because variation of ambient temperature causes dope viscosity.Coating is used thickening material provided by the invention to use without adjusting to fill a prescription can realize under the environment of differing temps.Polyurethane associative thickener provided by the invention is a kind of bright market prospects and superior thickening material of over-all properties of having.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a preparation method for polyurethane associative thickener, is characterized in that, described method comprises:
At 50 ~ 150 ℃, make dibasic alcohol and vulcabond complete reaction under catalyst action of dehydration, obtain intermediate;
Described intermediate is mixed according to the ratio of mol ratio 1:2 with end-capping reagent, and at 30 ~ 100 ℃, reaction obtains polyurethane associative thickener, and wherein, the structural formula of described end-capping reagent is as follows:
In structural formula: R is epoxy group(ing), alkane or phenyl ring;
X is 0 ~ 10 integer;
Y is 0 ~ 10 integer;
Z is 0 ~ 30 integer.
2. the preparation method of polyurethane associative thickener as claimed in claim 1, is characterized in that, the dewatering of described dibasic alcohol specifically comprises:
Dibasic alcohol material is put into the reactor with prolong and thermometer, under vacuum state, at 80 ~ 120 ℃, dewater 2 ~ 4 hours, arrive material moisture lower than 0.5%.
3. the preparation method of polyurethane associative thickener as claimed in claim 2, is characterized in that, described at 50 ~ 150 ℃, makes dibasic alcohol and vulcabond complete reaction under catalyst action of dehydration, obtains intermediate, specifically comprises:
In reactor, add catalyzer, at 50 ℃ ~ 150 ℃, in the dibasic alcohol of dehydration, drip vulcabond while stirring, after dripping, react 1～24 hour, follow the tracks of NCO group in detection reaction system, when the quality percentage composition of NCO group is less than or equal to 1.2%, finish reaction, obtain intermediate.
4. the preparation method of polyurethane associative thickener as claimed in claim 3, it is characterized in that, described at 30 ~ 100 ℃ reaction obtain polyurethane associative thickener, specifically comprise: at 30 ~ 100 ℃, react 2 ~ 12 hours, follow the tracks of NCO group in detection reaction system, when the quality percentage composition of NCO group is less than 0.05%, finish reaction, obtain polyurethane associative thickener.
5. the preparation method of polyurethane associative thickener as claimed in claim 1, is characterized in that, described dibasic alcohol is that molecular weight is 10000 ~ 50000 polyoxyethylene glycol.
6. the preparation method of polyurethane associative thickener as claimed in claim 1, it is characterized in that, described vulcabond is isophorone diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or diphenylmethanediisocyanate.
7. the preparation method of polyurethane associative thickener as claimed in claim 1, is characterized in that, the mol ratio of described vulcabond and described dibasic alcohol is 1 ~ 2:1.
8. the preparation method of polyurethane associative thickener as claimed in claim 1, is characterized in that, described catalyzer is one or more combinations in stannous octoate, dibutyl tin laurate, dibutyl tin maleate, zinc octoate.
9. the preparation method of polyurethane associative thickener as claimed in claim 1, is characterized in that, the quality of used catalyst is 0.05 ~ 10% of vulcabond and dibasic alcohol total mass.
10. the application of the polyurethane associative thickener of preparing according to the method described in claim 1 ~ 9 any one claim in emulsion paint, varnish, tackiness agent, leather, papermaking, printing and dyeing, ink, makeup and personal care articles.
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| CN107001564A (en) * | 2014-12-19 | 2017-08-01 | 可泰克斯公司 | Thickener for water-based system, the preparation containing it and its purposes |
| CN107207691A (en) * | 2014-12-04 | 2017-09-26 | 路博润先进材料公司 | The viscosity modifier of composition containing organic phase |
| CN108026234A (en) * | 2015-10-05 | 2018-05-11 | 可泰克斯公司 | Thickener for water-based system, contain its preparation and its purposes |
| CN109705649A (en) * | 2018-12-11 | 2019-05-03 | 万华化学（宁波）有限公司 | Synergistic mixtures solution containing non-ionic polyurethane compound and the metal substrate water paint containing it |
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| CN106957557A (en) * | 2017-03-27 | 2017-07-18 | 上海优卡化工科技有限公司 | It is a kind of for association thickener of aqueous UV polyurethane coatings and preparation method thereof |
| CN110785448A (en) * | 2017-04-13 | 2020-02-11 | 毕克化学有限公司 | Polymers suitable as thickeners |
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| US11377553B2 (en) | 2017-04-13 | 2022-07-05 | Byk-Chemie Gmbh | Polymer suitable as a thickener |
| US10884182B2 (en) | 2017-06-02 | 2021-01-05 | Dsm Ip Assets B.V. | Thermally resistant radiation curable coatings for optical fiber |
| US11256028B2 (en) | 2017-06-02 | 2022-02-22 | Covestro (Netherlands) B.V. | Thermally resistant radiation curable coatings for optical fiber |
| US11952453B2 (en) | 2018-06-01 | 2024-04-09 | Covestro (Netherlands) B.V | Radiation curable compositions for coating optical fiber and the coatings produced therefrom |
| CN109705649A (en) * | 2018-12-11 | 2019-05-03 | 万华化学（宁波）有限公司 | Synergistic mixtures solution containing non-ionic polyurethane compound and the metal substrate water paint containing it |
| CN113480931A (en) * | 2021-07-26 | 2021-10-08 | 清远市美佳乐环保新材股份有限公司 | Easily volatile waterborne polyurethane coating |
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| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 516123 tuguawei Industrial Zone, Yuanzhou Town, BOLUO County, Huizhou City, Guangdong Province Patentee after: Guangdong Baibaishun Technology Co.,Ltd. Country or region after: China Address before: 516123 No. 488, tkau Wei Industrial Zone, Yuanzhou Town, Boluo County, Huizhou, Guangdong Patentee before: HUIZHOU FEIKAI NEW MATERIAL Co.,Ltd. Country or region before: China |