CN107722225A - A kind of branching type water-based polyurethane associative thickener and preparation method thereof - Google Patents
A kind of branching type water-based polyurethane associative thickener and preparation method thereof Download PDFInfo
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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Abstract
The present invention discloses a kind of branching type water-based polyurethane associative thickener and preparation method thereof, comprises the following steps：Isocyanate solution is added drop-wise in the polyethylene glycol after dehydration and carries out polymerisation, performed polymer is made；Add catalyst and long chain alkanol carries out half end capping reaction；After being cooled to 50 ~ 80 DEG C, add chain extender and carry out chain extending reaction, obtain branching type water-based polyurethane associative thickener.Polyurethane associative thickener structure prepared by the present invention has a plurality of hydrophobicity long-chain, the molecular weight of molecule is larger, and the hydrophobic association type network structure more completely stablized can be formed in aqueous phase or emulsion system so that it has stronger thickening properties and preferable stability.
Description
Technical field
The present invention relates to a kind of thickener, more particularly to a kind of branching type water-based polyurethane associative thickener and its system
Preparation Method.
Background technology
Aqueous polyurethane association thickener is a kind of emerging environmentally friendly thickener, its property in the solution
Similar to surfactant, it is by the polymer of oleophylic-Hydrophile-Lipophile three block structure composition.Due to its unique molecule
Structure so that its mechanism thickened, rheological characteristic etc. are all different from traditional thickener, compared to traditional thickener, aqueous polyurethane
The thickening capabilities of association thickener are strong, and levelability and storage stability are good, and are not easy mildew, the features such as film richness is high,
Get more and more people's extensive concerning.
The structure of traditional polyurethane associative thickener is relatively simple, typically the isocyanates by excess and poly- second two
Alcohol reacts the performed polymer prepared, and then the alkanol of long-chain carries out the linear polyester association thickener that end-blocking is prepared.This
Kind straight chain type polyurethane associative thickener is the structure that both ends carry hydrophobic grouping, and what it was formed in emulsion system is 2 points
The mode of association reaches thickening effect, and its thickening effect is easily affected by temperature and is deteriorated.
Patent CN 101096475A disclose a kind of preparation method of line style aqueous polyurethane thickener, synthesized by it
Polyurethane thickener belongs to the polyurethane thickener of traditional alkyl chain end-blocking, and its thickening effect is general, and the emulsion after thickening
Storage stability is bad.In polyurethane associative thickener, the heat resistance and salt tolerance of hydrophobic grouping rises to thickening properties to be dominated, and
Multiple spot associative structure is better than traditional linear polyurethane thickener.
Isocyanates and polyether Glycols reaction are prepared performed polymer by patent CN 101633718A, are then dredged homemade
Water-based glycol introduces performed polymer and carries out chain extension, and then alkylol carries out the polyurethane thickener that end-blocking is prepared for combed, due to dredging
The preparation of water-based glycol is complicated, it is difficult to applied to reality.
Patent CN 104211941A disclose a kind of preparation method of star-like polyurethane thickener, are opened using oxirane
Then cyclization reacts synthesis star polyurethane associative thickener, it is thickened into star-like polyethylene glycol with alkyl isocyanate
Effect and stability are all improved.But the synthesis of its hydrophobic diol and star polyethylene glycol is relatively complicated, practical application ratio
It is more difficult.
The content of the invention
The purpose of the present invention is on the basis of conventional urethane thickener synthesis technique, there is provided a kind of stability is good, increases
Branching type water-based polyurethane associative thickener of thick excellent performance and preparation method thereof.
A kind of preparation method of branching type water-based polyurethane associative thickener, comprises the following steps：
(1) isocyanate solution is added drop-wise in the polyethylene glycol after dehydration and carries out polymerisation, performed polymer is made；
(2) add catalyst and long chain alkanol carries out half end capping reaction；
(3) after being cooled to 50~80 DEG C, add chain extender and carry out chain extending reaction, obtain branching type water-based polyurethane association type and increase
Thick dose.
Further scheme, the polymerisation in the step (1) is in nitrogen atmosphere, under agitation, by isocyanide
Acid esters solution is added drop-wise in dehydration polyethylene glycol, is dripped off and is incubated 10~40min after 40~60 DEG C, then heats to 70~110
DEG C 2~5h is reacted again, obtain performed polymer.
Further scheme, the solvent in the isocyanate solution is acetone, MEK or DMF；It is different
Cyanate and-NCO/-OH in polyethylene glycol mol ratio are 1~2:1.
Further scheme, the isocyanates are selected from IPDI, hexamethylene diisocyanate, toluene
Diisocyanate, 4,4 ＇-methyl diphenylene diisocyanate, 2,6- diisocyanate methylhexanoic acids ester, methylcyclohexyl two are different
Cyanate, 4,4 ＇-dicyclohexyl methyl hydride diisocyanate, XDI, the diisocyanate of naphthalene -1,5, tetramethyl
One or more in base dimethylene diisocyanate.
Further scheme, the polyethylene glycol after the middle dehydration of the step (1) is to add polyethylene glycol in reactor, heating
Carried out to 100~120 DEG C obtained by 2~5h of vacuum dehydration；The molecular weight polyethylene glycol is preferably 2000~8000g/mol.
Further scheme, the long chain alkanol in the step (2) are the straight-chain alkyl alcohol of C8~18, long chain alkanol and poly- second
The ratio between amount of material of glycol is 1~2:1；
The catalyst is one in dibutyl tin laurate, stannous octoate, dibutyl tin maleate, zinc octoate
Kind is several, and the addition of catalyst is the 0.05~5% of polyethylene glycol and isocyanates gross mass.
Further scheme, the time of chain extending reaction is 2~6h in the step (3), and described chain extender is branching type core
The ratio between amount of material of B, isocyanates and chain extender is 2：0.1~1.
Further scheme, the branching type core B are that DMPA (dimethyl propylamine) DMF solution is slowly dropped into IPDI
In (IPDI), 70~90 DEG C of 1~3h of reaction are warming up to；Then it is placed in ice salt bath, control reaction
Temperature in system is -5~0 DEG C；The DMF solution of DEOA (diethanol amine) is slowly added dropwise again, 1~3h is dripped off, after reaction terminates
Branching type core B is obtained, its course of reaction is as follows：
The course of reaction of the present invention is as follows：
Another goal of the invention of the present invention is to provide branching type water-based polyurethane association type prepared by above-mentioned preparation method
Thickener.The molecular structure and performance of the branching type water-based polyurethane associative thickener of the present invention are can be by poly- second two
The molecular weight of alcohol, the structure of end-capping reagent long chain alkanol are adjusted.
Aqueous polyurethane association thickener prepared by the present invention can be applied to the thickening of Aquo System, and Aquo System includes
Emulsion paint, adhesive, leather, papermaking, printing and dyeing, varnish, cosmetic formulations and personal care product.
Polyurethane associative thickener structure synthesized by the present invention has a plurality of hydrophobicity long-chain, and molecular weight is larger, and
More complete and stable hydrophobic association type network structure can be formed in aqueous phase or emulsion system so that it has stronger increasing
Consistence can be with preferable stability.So there is polyurethane associative thickener prepared by the present invention thickening well to imitate to emulsion
Fruit, the viscosity of emulsion can be effectively improved at lower levels, and it is lower with high viscosity, high shear with low-shearing force effect
Under power effect the characteristics of low working viscosity, meet the application requirement to thickener, and cost needed for synthesis is relatively low, has preferable
Application prospect.
The relatively existing technology of the present invention has the following advantages and beneficial effect：
1st, the present invention prepares performed polymer using isocyanates and polyethylene glycol, carries out half end capping reaction with long chain alkanol, so
Afterwards using branching type polyalcohol progress chain extension is formed with certainly, a kind of branching type water-based polyurethane associative thickener is prepared for.It is this
There is a plurality of hydrophobic segment on the molecular structure of branching type water-based polyurethane associative thickener, in aqueous phase or emulsion system,
It mutually can associate to form micella between hydrophobic grouping or between hydrophobic grouping and latex particle, the hydrophobic end group of micella end is again
It can be associated with the hydrophobic end group of other micellas, multiple spot association to each other to form more complete space in system
Network structure, so as to significantly improve the viscosity of emulsion under low concentration；And intermolecular association conciliates association again
So that the system after thickening has the characteristic of the low working viscosity under high viscosity and high shear forces under low sheraing effect.
2nd, the present invention can be according to the requirement of application, the structure of molecular weight, end-capping reagent long chain alkanol to polyethylene glycol etc.
It is adjusted, so as to adjust the structure of prepared branching type water-based polyurethane associative thickener, that is, adjusts thickener
Thickening properties.As isocyanates, chain extender and end-capping reagent in embodiment 1, embodiment 2, embodiment 3 in the present invention species not
Become, only change the molecular weight of polyethylene glycol, so as to just prepare the branching type water-based poly- ammonia of three kinds of different relative molecular masses
Ester association thickener, and the thickening properties of three kinds of polyurethane associative thickeners because molecular weight difference it is also different.
Brief description of the drawings
Fig. 1 is the infrared spectrum of branching type water-based polyurethane associative thickener prepared by embodiment 1-6.
Fig. 2 is the Aqueous Solution Viscosity of branching type water-based polyurethane associative thickener prepared by embodiment 1 with shear rate
Variation diagram.
Embodiment
The present invention is expanded on further with reference to embodiment, but embodiments of the present invention are not limited to that.
Branching type core B is that DMPA (dimethyl propylamine) DMF solution is slowly dropped into IPDI is (different in embodiments below
Isophorone diisocyanate) in, it is warming up to 70~90 DEG C of 1~3h of reaction；Then it is placed in ice salt bath, controls reaction system
In temperature be -5~0 DEG C；The DMF solution of DEOA (diethanol amine) is slowly added dropwise again, 1~3h is dripped off, and reaction must prop up after terminating
Change type core B, its course of reaction are as follows：
Embodiment 1：
The preparation method of branching type water-based polyurethane associative thickener is as follows in the present embodiment：
(1) dewater treatment
The polyethylene glycol 50g that molecular weight is 6000g/mol is added in reactor, is warming up to 110 DEG C of vacuum dehydration 3h；
(2) pre-polymerization
Polyethylene glycol after dehydration is cooled to 55 DEG C, under nitrogen protection, agitation and dropping IPDI
(IPDI) DMF solution, the quality of IPDI is 3.70g, drips off and is incubated 30min, Ran Housheng after 55 DEG C
Temperature obtains performed polymer to 80 DEG C of reaction 3h.
(3) half end capping reactions
After the completion of prepolymerization reaction, 80 DEG C of the temperature of system is kept, 2.02g hexadecanols and 0.06g bis- are added into system
Dibutyl tin laurate carries out half end capping reaction, 80 DEG C of reaction 3h.
(4) chain extending reaction
After the completion of half end capping reaction, 1.64g branching type cores B, 80 DEG C of chain extending reaction 3h are added to system, after reaction terminates,
Sample is transferred to surface plate, then 70 DEG C of vacuum drying 24h obtain branching type water-based polyurethane associative thickener.
After the sample heating melting of branching type water-based polyurethane associative thickener prepared by the present embodiment 1, glass is used
Glass capillary is evenly coated in KBr tablettings, utilizes U.S. Nicolet companies Nexus870 type Fourier transform infrared spectrum instrument pair
Sample carries out infrared analysis, the scope of measure：400-4000cm-1, the infrared spectrogram of sample is obtained, as shown in Figure 1.Can from Fig. 1
To find out, 2270~2280cm-1The absworption peak at place disappears substantially, in explanation system-NCO group reacts completely；3342cm-1
The absworption peak at place is caused by the stretching vibration of N-H keys in the carbamate that is generated, while 1718cm-1The absworption peak at place
For the characteristic absorption peak of C=O stretching vibrations in carbamate, herein peak shape enhancing, explanation-OH and-NCO reactions generate ammonia
Carbamate.
Branching type water-based polyurethane associative thickener sample prepared by the present embodiment 1 is dissolved in by ethylene glycol and water by matter
Amount is than being 1:In the cosolvent of 1 composition, 60 DEG C of water bath with thermostatic control insulation 10min are subsequently placed in, treats that sample dissolves, stirs and evenly mixs, match somebody with somebody
Mass fraction processed is 10% thickener soln.Then Malvern company of Britain Gemini-HR Nano type rotational rheometers are utilized
Rheology measurement (its shear rate change scope is carried out to it：0.01~1000s-1, test temperature：25 DEG C), as a result such as Fig. 2 institutes
Show.
As seen from Figure 2, thickener soln keeps higher viscosity in low shear rate, in the presence of high shear force
Viscosity is thinning.Understood according to the analysis of polyurethane associative thickener thickening mechanism, the parent of the polyurethane associative thickener aqueous solution
Water segment can form close ring, and hydrophobic ending group can associate to form micelle inner core；If being isolated between each micella, it is difficult between micella
Associate with each other, solution viscosity is smaller；When intermolecular hydrophobic association micella is connected with each other, intermolecular association networks could shape
Into the viscosity of the aqueous solution will increase.Under the conditions of it extraneous shearing force be present, hydrophobic ending group solves the speed of association from micella
More than the speed associated again, the association networks of formation are destroyed, and system viscosity reduces rapidly.
Embodiment 2：
The preparation method of branching type water-based polyurethane associative thickener is as follows in the present embodiment：
(1) dewater treatment
The polyethylene glycol 50g that molecular weight is 2000g/mol is added in reactor, is warming up to 110 DEG C of vacuum dehydration 3h；
(2) pre-polymerization
Polyethylene glycol after dehydration is cooled to 55 DEG C, under nitrogen protection, agitation and dropping IPDI
(IPDI) acetone soln, the quality of IPDI is 11.1g, drips off and is incubated 30min, Ran Housheng after 55 DEG C
Temperature obtains performed polymer to 80 DEG C of reaction 3h.
(3) half end capping reactions
After the completion of prepolymerization reaction, 80 DEG C of the temperature of system is kept, 6.06g hexadecanols and 0.06g bis- are added into system
Dibutyl tin laurate carries out half end capping reaction, 80 DEG C of reaction 3h.
(4) chain extending reaction
After the completion of half end capping reaction, 4.93g branching types core B, chain extending reaction 3h are added to system, after reaction terminates, by sample
Product are transferred to surface plate, and then 70 DEG C of vacuum drying 24h obtain branching type water-based polyurethane associative thickener.
After the sample heating melting of branching type water-based polyurethane associative thickener prepared by the present embodiment 2, glass is used
Glass capillary is evenly coated in KBr tablettings, utilizes U.S. Nicolet companies Nexus870 type Fourier transform infrared spectrum instrument pair
Sample carries out infrared analysis, the scope of measure：400-4000cm-1, the infrared spectrogram of sample is obtained, as shown in Figure 1.Can by Fig. 1
To find out, 2270~2280cm-1The absworption peak at place disappears substantially, in explanation system-NCO group reacts completely.3342cm-1
The absworption peak at place is caused by the stretching vibration of N-H keys in the carbamate that is generated, while 1718cm-1The absworption peak at place
For the characteristic absorption peak of C=O stretching vibrations in carbamate, herein peak shape enhancing, explanation-OH and-NCO reactions generate ammonia
Carbamate.
Embodiment 3
The preparation method of branching type water-based polyurethane associative thickener is as follows in the present embodiment：
(1) dewater treatment
The polyethylene glycol 50g that molecular weight is 4000g/mol is added in reactor, is warming up to 110 DEG C of vacuum dehydration 3h；
(2) pre-polymerization
Polyethylene glycol after dehydration is cooled to 55 DEG C, under nitrogen protection, agitation and dropping IPDI
(IPDI) acetone soln, the quality of IPDI is 5.56g, drips off and is incubated 30min, Ran Housheng after 55 DEG C
Temperature obtains performed polymer to 80 DEG C of reaction 3h.
(3) half end capping reactions
After the completion of prepolymerization reaction, 80 DEG C of the temperature of system is kept, 3.03g hexadecanols and 0.06g bis- are added into system
Dibutyl tin laurate carries out half end capping reaction, 80 DEG C of reaction 3h.
(4) chain extending reaction
After the completion of half end capping reaction, 1.64g self-control branching type core B, chain extending reaction 3h are added to system, after reaction terminates,
Sample is transferred to surface plate, then 70 DEG C of vacuum drying 24h obtain branching type water-based polyurethane associative thickener.
After the sample heating melting of branching type water-based polyurethane associative thickener prepared by the present embodiment 3, glass is used
Glass capillary is evenly coated in KBr tablettings, utilizes U.S. Nicolet companies Nexus870 type Fourier transform infrared spectrum instrument pair
Sample carries out infrared analysis, the scope of measure：400-4000cm-1, the infrared spectrogram of sample is obtained, as shown in Figure 1.Can by Fig. 1
To find out, 2270~2280cm-1The absworption peak at place disappears substantially, in explanation system-NCO group reacts completely.3342cm-1
The absworption peak at place is caused by the stretching vibration of N-H keys in the carbamate that is generated, while 1718cm-1The absworption peak at place
For the characteristic absorption peak of C=O stretching vibrations in carbamate, herein peak shape enhancing, explanation-OH and-NCO reactions generate ammonia
Carbamate.
Embodiment 4：
The preparation method of branching type water-based polyurethane associative thickener is as follows in the present embodiment：
(1) dewater treatment
The polyethylene glycol 50g that molecular weight is 8000g/mol is added in reactor, is warming up to 110 DEG C of vacuum dehydration 3h；
(2) pre-polymerization
Polyethylene glycol after dehydration is cooled to 55 DEG C, under nitrogen protection, agitation and dropping IPDI
(IPDI) acetone soln, the quality of IPDI is 2.78g, drips off and is incubated 30min, Ran Housheng after 55 DEG C
Temperature obtains performed polymer to 80 DEG C of reaction 3h.
(3) half end capping reactions
After the completion of prepolymerization reaction, 80 DEG C of the temperature of system is kept, 1.51g hexadecanols and 0.06g bis- are added into system
Dibutyl tin laurate carries out half end capping reaction, 80 DEG C of reaction 3h.
(4) chain extending reaction
After the completion of half end capping reaction, 1.23g branching types core B, chain extending reaction 3h are added into system, will after reaction terminates
Sample is transferred to surface plate, and then 70 DEG C of vacuum drying 24h obtain branching type water-based polyurethane associative thickener.
After the sample heating melting of branching type water-based polyurethane associative thickener prepared by the present embodiment 4, glass is used
Glass capillary is evenly coated in KBr tablettings, utilizes U.S. Nicolet companies Nexus870 type Fourier transform infrared spectrum instrument pair
Sample carries out infrared analysis, the scope of measure：400-4000cm-1, the infrared spectrogram of sample is obtained, as shown in Figure 1.Can by Fig. 1
To find out, 2270~2280cm-1The absworption peak at place disappears substantially, in explanation system-NCO group reacts completely.3342cm-1
The absworption peak at place is caused by the stretching vibration of N-H keys in the carbamate that is generated, while 1718cm-1The absworption peak at place
For the characteristic absorption peak of C=O stretching vibrations in carbamate, herein peak shape enhancing, explanation-OH and-NCO reactions generate ammonia
Carbamate.
Embodiment 5
The preparation method of branching type water-based polyurethane associative thickener is as follows in the present embodiment：
(1) dewater treatment
The polyethylene glycol 50g that molecular weight is 1000g/mol is added in reactor, is warming up to 100 DEG C of vacuum dehydration 5h；
(2) pre-polymerization
Polyethylene glycol after dehydration is cooled to 55 DEG C, under nitrogen protection, agitation and dropping toluene di-isocyanate(TDI) (TDI)
Ethyl ketone solution, the quality of toluene di-isocyanate(TDI) is 17.41g, drip off after 40 DEG C be incubated 40min, then heat to 70 DEG C
5h is reacted, obtains performed polymer.
(3) half end capping reactions
After the completion of prepolymerization reaction, 80 DEG C of the temperature of system is kept, 6.51g noctythiols is added into system and 0.06g is pungent
Sour stannous carries out half end capping reaction, 80 DEG C of reaction 3h.
(4) chain extending reaction
After the completion of half end capping reaction, 9.85g self-control branching type core B, chain extending reaction 3h are added to system, after reaction terminates,
Sample is transferred to surface plate, then 70 DEG C of vacuum drying 24h obtain branching type water-based polyurethane associative thickener.
After the sample heating melting of branching type water-based polyurethane associative thickener prepared by the present embodiment 5, glass is used
Glass capillary is evenly coated in KBr tablettings, utilizes U.S. Nicolet companies Nexus870 type Fourier transform infrared spectrum instrument pair
Sample carries out infrared analysis, the scope of measure：400-4000cm-1, the infrared spectrogram of sample is obtained, as shown in Figure 1.Can by Fig. 1
To find out, 2270~2280cm-1The absworption peak at place disappears substantially, in explanation system-NCO group reacts completely.3342cm-1
The absworption peak at place is caused by the stretching vibration of N-H keys in the carbamate that is generated, while 1718cm-1The absworption peak at place
For the characteristic absorption peak of C=O stretching vibrations in carbamate, herein peak shape enhancing, explanation-OH and-NCO reactions generate ammonia
Carbamate.
Embodiment 6
The preparation method of branching type water-based polyurethane associative thickener is as follows in the present embodiment：
(1) dewater treatment
The polyethylene glycol 50g that molecular weight is 10000g/mol is added in reactor, is warming up to 120 DEG C of vacuum dehydration 2h；
(2) pre-polymerization
Polyethylene glycol after dehydration is cooled to 55 DEG C, under nitrogen protection, agitation and dropping hexamethylene diisocyanate
(HDI) ethyl ketone solution, the quality of hexamethylene diisocyanate is 1.68g, drips off and is incubated 10min, Ran Housheng after 60 DEG C
Temperature obtains performed polymer to 110 DEG C of reaction 2h.
(3) half end capping reactions
After the completion of prepolymerization reaction, 80 DEG C of the temperature of system is kept, 1.36g octadecanols is added into system and 0.06g is mixed
Close dibutyl tin laurate and carry out half end capping reaction, 80 DEG C of reaction 3h with stannous octoate.
(4) chain extending reaction
After the completion of half end capping reaction, 0.985g self-control branching type core B, chain extending reaction 3h are added to system, after reaction terminates,
Sample is transferred to surface plate, then 70 DEG C of vacuum drying 24h obtain branching type water-based polyurethane associative thickener.
After the sample heating melting of branching type water-based polyurethane associative thickener prepared by the present embodiment 6, glass is used
Glass capillary is evenly coated in KBr tablettings, utilizes U.S. Nicolet companies Nexus870 type Fourier transform infrared spectrum instrument pair
Sample carries out infrared analysis, the scope of measure：400-4000cm-1, the infrared spectrogram of sample is obtained, as shown in Figure 1.Can by Fig. 1
To find out, 2270~2280cm-1The absworption peak at place disappears substantially, in explanation system-NCO group reacts completely.3342cm-1
The absworption peak at place is caused by the stretching vibration of N-H keys in the carbamate that is generated, while 1718cm-1The absworption peak at place
For the characteristic absorption peak of C=O stretching vibrations in carbamate, herein peak shape enhancing, explanation-OH and-NCO reactions generate ammonia
Carbamate.
Claims (9)
- A kind of 1. preparation method of branching type water-based polyurethane associative thickener, it is characterised in that：Comprise the following steps：（1）Isocyanate solution is added drop-wise in the polyethylene glycol after dehydration and carries out polymerisation, performed polymer is made；（2）Add catalyst and long chain alkanol carries out half end capping reaction；（3）After being cooled to 50 ~ 80 DEG C, add chain extender and carry out chain extending reaction, obtain branching type water-based polyurethane associative thickener.
- 2. preparation method according to claim 1, it is characterised in that：The step（1）In polymerisation be in nitrogen In atmosphere, under agitation, by isocyanate solution be added drop-wise to dehydration polyethylene glycol in, drip off after 40 ~ 60 DEG C be incubated 10 ~ 40min, then heat to 70 ~ 110 DEG C and react 2 ~ 5h again, obtain performed polymer.
- 3. preparation method according to claim 1 or 2, it is characterised in that：Solvent in the isocyanate solution is third Ketone, MEK or DMF；Isocyanates and-NCO/-OH in polyethylene glycol mol ratio are 1 ~ 2:1.
- 4. preparation method according to claim 1 or 2, it is characterised in that：It is different that the isocyanates is selected from isophorone two Cyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), 4,4 ＇-methyl diphenylene diisocyanate, the isocyanides of 2,6- bis- Acid esters methylhexanoic acid ester, Methylcyclohexyl diisocyanate, 4,4 ＇-dicyclohexyl methyl hydride diisocyanate, phenylenedimethylidyne two One or more in isocyanates, the diisocyanate of naphthalene -1,5, tetramethyl dimethylene diisocyanate.
- 5. preparation method according to claim 1, it is characterised in that：The step（1）Polyethylene glycol after middle dehydration is Polyethylene glycol is added in reactor, 100 ~ 120 DEG C is warming up to and carries out obtained by 2 ~ 5h of vacuum dehydration；The molecular weight polyethylene glycol Preferably 1000 ~ 10000g/mol.
- 6. preparation method according to claim 1, it is characterised in that：The step（2）In long chain alkanol for C8 ~ 18 The material of straight-chain alkyl alcohol, long chain alkanol and polyethylene glycol'sThe ratio between amount is 1 ~ 2:1；The catalyst be dibutyl tin laurate, stannous octoate, dibutyl tin maleate, one kind in zinc octoate or Several, the addition of catalyst is the 0.05 ~ 5% of polyethylene glycol and isocyanates gross mass.
- 7. preparation method according to claim 1, it is characterised in that：The step（3）The time of middle chain extending reaction be 2 ~ 6h, described chain extender are branching type core B, and the ratio between amount of material of isocyanates and chain extender is 2：0.1~1.
- 8. preparation method according to claim 7, it is characterised in that：The branching type core B is by DMPA（Dimethyl propylene Amine）DMF solution be slowly dropped to IPDI（IPDI）In, it is warming up to 70 ~ 90 DEG C of 1 ~ 3h of reaction；Then will It is placed in ice salt bath, and it is -5 ~ 0 DEG C to control the temperature in reaction system；DEOA is slowly added dropwise again（Diethanol amine）DMF it is molten Liquid, 1 ~ 3h are dripped off, and reaction obtains branching type core B after terminating.
- A kind of 9. branching type water-based polyurethane associative thickener prepared by preparation method as claimed in claim 1.
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| CN112961301A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Branched polyurethane thickener with ionized linear main chain and preparation method thereof |
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| CN112708095A (en) * | 2020-12-28 | 2021-04-27 | 华南理工大学 | Branched hydrophobic end modified association type water-based urethane thickener and preparation method and application thereof |
| CN112831010A (en) * | 2021-02-07 | 2021-05-25 | 湖北达雅生物科技股份有限公司 | Ionized multi-arm star-structured polyurethane thickener and preparation method thereof |
| CN112898530A (en) * | 2021-02-07 | 2021-06-04 | 武汉纺织大学 | Weak-ionic polyurethane thickener with side long-chain alkyl and preparation method thereof |
| CN112961317A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Star-shaped polyurethane thickener with anion-cation amphoteric ion core and preparation method thereof |
| CN112961301A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Branched polyurethane thickener with ionized linear main chain and preparation method thereof |
| CN112961317B (en) * | 2021-02-07 | 2022-06-10 | 武汉纺织大学 | Star-shaped polyurethane thickener with anion-cation amphoteric ion core and preparation method thereof |
| CN112961301B (en) * | 2021-02-07 | 2022-06-10 | 武汉纺织大学 | Branched polyurethane thickener with ionized linear main chain and preparation method thereof |
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Application publication date: 20180223 |