CN107141442A - A kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin - Google Patents
A kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin Download PDFInfo
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- CN107141442A CN107141442A CN201710536904.XA CN201710536904A CN107141442A CN 107141442 A CN107141442 A CN 107141442A CN 201710536904 A CN201710536904 A CN 201710536904A CN 107141442 A CN107141442 A CN 107141442A
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- 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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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin, belong to water paint industrial circle.Part polyether Glycols or polyester diol are substituted by terminal hydroxy liquid rubber to react under catalyst action with diisocyanate, and with hydrophilic chain extender and small molecule chain extender chain extension, after being neutralized through salt forming agent in water dispersion and emulsion, while add rear chain extender end-blocking after obtain.Terminal hydroxy liquid rubber is introduced into aqueous polyurethane system by the present invention by way of copolymerization, its longer non-polar carbon chains makes emulsion in film forming procedure because in hard section and soft segment microcell obvious microphase-separated can occur for the difference of polarity, so that aqueous polyurethane glued membrane produces rough surface, the effect of delustring is reached.Meanwhile, the water resistance of aqueous polyurethane can be improved by the ethylene linkage of terminal hydroxy liquid rubber strong-hydrophobicity.Preparation technology of the present invention is simple, and safety and environmental protection, cost is relatively low, with higher industrial application value.
Description
Technical field
The present invention relates to a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin, belong to water paint
Industrial circle.
Background technology
Aqueous polyurethane have it is nontoxic, nonflammable, do not pollute, it is safe and reliable, easy to operate and modified the features such as, therefore applying
The fields such as material, adhesive and leather finishing agent are widely used.But compared to traditional solvent borne polyurethane, still there is some shortcomings
And defect.Due to introducing hydrophilic radical in aqueous polyurethane main chain, so its water resistance is relatively poor；In addition, aqueous poly- ammonia
The molecular weight of ester is lower than solvent borne polyurethane so that mechanical property and heat resistance have much room for improvement.
Leather finishing agent can be modified the surface property of leather substance to meet the demand of various applications.Therefore,
Feature leather finishing agent coating receives extensive concern in recent years.The coating of delustring has graceful, soft, natural outward appearance, symbol
The life requirement of present people is closed, the favor of consumers in general is received.Synthesis matting resin can avoid directly adding flatting silica
The defects such as the stability of emulsion poor, emulsion viscosity is raised, the scratch resistance decline of glued membrane that are brought, and then receive extensive pass
Note.Chinese patent 104164785A discloses a kind of aqueous frosting inorganic agent of use for synthetic leather and its application process, the patent
Aqueous polyurethane, sodium alginate soln, polyurethane fine hair powder, casein finishing agent, crosslinking agent and water are mixed to form synthetic leather table
Face inorganic agent, is then covered with paint, lacquer, colour wash, etc. synthetic leather, and the surface of delustring is obtained after drying.This method substantially still utilizes physics side
Method reaches delustring, while the aziridine crosslinker used in this method has high toxicity, human body is potentially dangerous.Chinese patent
103740250A discloses a kind of preparation method from extinction type leather waterborne polyurethane coating agent, and this method has synthesized a kind of tool
The polyurethane component A of crosslinking structure greater particle size, makes it be mixed with the less B component of particle diameter, the A groups in film forming procedure
Floated on the surface on point, make film that there is higher roughness to reach extinction effect.This method needs first to synthesize two kinds of aqueous polyurethanes, then
By its physical blending, preparation technology is complex.
The content of the invention
It is an object of the invention to provide a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin.The party
The characteristics of method includes carbon-carbon double bond and two hydroxyls using terminal hydroxy liquid rubber backbone, by terminal hydroxy group liquid by way of copolymerization
Body rubber is introduced into aqueous polyurethane system, the longer non-polar carbon chains of terminal hydroxy liquid rubber make emulsion film forming procedure due to
In hard section and soft segment microcell obvious microphase-separated can occur for the difference of polarity, so that aqueous polyurethane glued membrane generation surface is thick
It is rough, reach the effect of delustring.Meanwhile, the water-fast of aqueous polyurethane can be improved by the ethylene linkage of terminal hydroxy liquid rubber strong-hydrophobicity
Property.
The purpose of the present invention is achieved through the following technical solutions.
A kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin, by terminal hydroxy group by way of copolymerization
Liquid rubber is introduced into aqueous polyurethane system, and the longer non-polar carbon chains of terminal hydroxy liquid rubber make emulsion exist in film forming procedure
Obvious microphase-separated can occur for hard section and soft segment microcell, so that aqueous polyurethane glued membrane produces rough surface, realize delustring
Purpose；
A kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin, is comprised the following steps that：
Step 1: the terminal hydroxy liquid rubber and polyether Glycols after vaccum dewatering or polyester diol are mixed,
Diisocyanate is added under controlled atmosphere and mechanical agitation, reacts to the content of remaining isocyano and reaches under catalyst action
Product A is obtained after to theoretical value a；The quality of terminal hydroxy liquid rubber account for polyether Glycols or polyester diol quality 10~
50%.
Step 2: hydrophilic chain extender is added in the product A that step one is obtained, continue to react to remaining isocyano
Content is reached after theoretical value b, obtains product B；The quality of hydrophilic chain extender accounts for the 3~10% of performed polymer gross mass.
Step 3: small molecule chain extender is added in the product B that step 2 is obtained, continue to react to remaining isocyano
Content reach after theoretical value c, obtain product C；The quality of small molecule chain extender accounts for the 1~3% of performed polymer gross mass；Define R
For isocyano in performed polymer with Step 1: Step 2: in step 3 the material of all hydroxyls amount ratio, then need R ＞ 1.
Step 4: product C is down into room temperature, salt forming agent is then added, until the neutralization of salt forming agent and hydrophilic chain extender is anti-
Should be complete, obtain performed polymer；The amount ratio of the material of salt forming agent and hydrophilic chain extender is 1:1.
Step 5: the performed polymer obtained by step 4 is scattered emulsified in high speed, chain extension after emulsification is added immediately after starting
Agent, obtains terminal hydroxy liquid modified rubber aqueous polyurethane matting resin；Amido and remaining isocyanide in performed polymer in rear chain extender
The amount ratio of the material of acid group is 1:1.
Step 1: the calculation formula of the isocyano theoretical value described in two, three is respectively：
Wherein n(NCO)The amount (mol) of the material of isocyano in=diisocyanate；n1(OH)=terminal hydroxy liquid rubber
The amount (mol) of the material of middle hydroxyl；n2(OH) amount (mol) of the material of hydroxyl in=polyether Glycols or polyester diol；n3
(OH) amount (mol) of the material of hydroxyl in=hydrophilic chain extender；n4(OH) (mol) of the material of hydroxyl in=chain extender；M(NCO)
The molal weight of=isocyano, is fixed value 42g/mol；The gross mass (g) of m=performed polymers.
Terminal hydroxy liquid rubber described in step one includes end hydroxy butadiene (HTPB) and hydroxyl terminated polyisoprene
(HTPI)。
Polyether Glycols described in step one or polyester diol include PTMG (PTMG), polyadipate second
Glycol propylene glycol ester (PEPA) or polyadipate ethylene glycol DOPCP (PHNA).
Diisocyanate described in step one includes isoflurane chalcone diisocyanate (IPDI), toluene di-isocyanate(TDI)
(TDI), 1,6- hexyl diisocyanates (HDI), methyl diphenylene diisocyanate (MDI) or the isocyanic acid of tetramethyl-ring hexyl two
Ester (TMXDI).
Catalyst described in step one includes dibutyl tin laurate (DBTDL), tert-butyl group tin or organic bismuth catalyst.
Hydrophilic chain extender described in step 2 includes dihydromethyl propionic acid (DMPA) or 2,2- dimethylolpropionic acids.
Small molecule chain extender described in step 3 includes 1,4- butanediols (BDO) or 1,6-HD (HDO).
Salt forming agent described in step 4 includes triethylamine (TEA) or tri-n-butylamine.
Rear chain extender described in step 5 includes ethylenediamine (EDA), 1,6- hexamethylene diamines or hydrazine hydrate.
Temperature when adding diisocyanate described in step one is 70~90 DEG C；Step one first cools after obtaining product A
Hydrophilic chain extender is added after 20~30 DEG C, 70~90 DEG C of reactions are then warming up to；The step 3 is maintained at 70~90 DEG C
Reaction
Beneficial effect
1st, the present invention substitutes part polyether Glycols or polyester diol by terminal hydroxy liquid rubber, in the way of copolymerization
It is incorporated into aqueous polyurethane, good extinction effect is reached after emulsion film forming, while significantly improves the water resistance of glued membrane.Wherein
60 ° of glossiness minimum 2.6, water absorption rate minimum 3.7%.
2nd, preparation technology of the present invention is simple, and safety and environmental protection, cost is relatively low, with higher industrial application value.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
In equipped with agitator, reflux condensing tube, the reactor of thermometer add vaccum dewatering after 21.8g PTMG and
2.4g HTPB, add 14.2g IPDI and 0.01g catalyst DBTDL reactions 2h in 80 DEG C under nitrogen protection；It is cooled to 60 DEG C
1.5g DMPA and appropriate solvent butanone are added, 80 DEG C of reaction 3h are warming up to；Add after 1.3g BDO reactions 1h, cool to room
Temperature adds 1.1g TEA neutralization reaction 30min, obtains Waterborne Polyurethane Prepolymer；By performed polymer stir speed (S.S.) be 2500r/
The emulsified 20min of min, 1.8g EDA are added after first adding 128.7g deionized waters immediately, make remaining-NCO reactions in emulsion
Completely.Butanone is evaporated off in 40 DEG C of backspins in emulsion, terminal hydroxy liquid modified rubber aqueous polyurethane matting resin emulsion is obtained.
Take appropriate emulsion casting film-forming in Teflon mould plate, drying at room temperature 7d dries 24h at 70 DEG C, obtains terminal hydroxy group liquid
Body rubber modified aqueous polyurethane matting resin glued membrane.
Embodiment 2
In equipped with agitator, reflux condensing tube, the reactor of thermometer add vaccum dewatering after 19.8g PEPA and
5.0g HTPB, add 13.8g IPDI and 0.01g catalyst DBTDL reactions 2h in 85 DEG C under nitrogen protection；It is cooled to 65 DEG C
1.5g DMPA and appropriate solvent butanone are added, 85 DEG C of reaction 3h are warming up to；Add after 1.3g BDO reactions 1h, cool to room
Temperature adds 1.1g TEA neutralization reaction 30min, obtains Waterborne Polyurethane Prepolymer；By performed polymer stir speed (S.S.) be 2500r/
The emulsified 20min of min, 1.8g EDA are added after first adding 128.7g deionized waters immediately, make remaining-NCO reactions in emulsion
Completely.Butanone is evaporated off in 40 DEG C of backspins in emulsion, terminal hydroxy liquid modified rubber aqueous polyurethane matting resin emulsion is obtained.
Take appropriate emulsion casting film-forming in Teflon mould plate, drying at room temperature 7d dries 24h at 70 DEG C, obtains terminal hydroxy group liquid
Body rubber modified aqueous polyurethane matting resin glued membrane.
Embodiment 3
In equipped with agitator, reflux condensing tube, the reactor of thermometer add vaccum dewatering after 17.7g PHNA and
7.6g HTPB, add 13.3g IPDI and 0.01g catalyst DBTDL reactions 2h in 90 DEG C under nitrogen protection；It is cooled to 60 DEG C
1.5g DMPA and appropriate solvent butanone are added, 90 DEG C of reaction 3h are warming up to；Add after 1.3g BDO reactions 1h, cool to room
Temperature adds 1.1g TEA neutralization reaction 30min, obtains Waterborne Polyurethane Prepolymer；By performed polymer stir speed (S.S.) be 2500r/
The emulsified 20min of min, 1.7g EDA are added after first adding 128.7g deionized waters immediately, make remaining-NCO reactions in emulsion
Completely.Butanone is evaporated off in 40 DEG C of backspins in emulsion, terminal hydroxy liquid modified rubber aqueous polyurethane matting resin emulsion is obtained.
Take appropriate emulsion casting film-forming in Teflon mould plate, drying at room temperature 7d dries 24h at 70 DEG C, obtains terminal hydroxy group liquid
Body rubber modified aqueous polyurethane matting resin glued membrane.
Embodiment 4
In equipped with agitator, reflux condensing tube, the reactor of thermometer add vaccum dewatering after 18.2g PTMG and
4.6g HTPI, add 15.0g IPDI and 0.01g catalyst DBTDL reactions 2h in 75 DEG C under nitrogen protection；It is cooled to 50 DEG C
1.5g DMPA and appropriate solvent butanone are added, 75 DEG C of reaction 3h are warming up to；Add after 1.3g BDO reactions 1h, cool to room
Temperature adds 1.1g TEA neutralization reaction 30min, obtains Waterborne Polyurethane Prepolymer；By performed polymer stir speed (S.S.) be 2500r/
The emulsified 20min of min, 1.3g EDA are added after first adding 128.7g deionized waters immediately, make remaining-NCO reactions in emulsion
Completely.Butanone is evaporated off in 40 DEG C of backspins in emulsion, terminal hydroxy liquid modified rubber aqueous polyurethane matting resin emulsion is obtained.
Take appropriate emulsion casting film-forming in Teflon mould plate, drying at room temperature 7d dries 24h at 70 DEG C, obtains terminal hydroxy group liquid
Body rubber modified aqueous polyurethane matting resin glued membrane.
Embodiment 5
In equipped with agitator, reflux condensing tube, the reactor of thermometer add vaccum dewatering after 16.7g PEPA and
4.2g HTPI, add 16.3g IPDI and 0.01g catalyst DBTDL reactions 2h in 80 DEG C under nitrogen protection；It is cooled to 50 DEG C
1.5g DMPA and appropriate solvent butanone are added, 80 DEG C of reaction 3h are warming up to；Add after 1.3g BDO reactions 1h, cool to room
Temperature adds 1.1g TEA neutralization reaction 30min, obtains Waterborne Polyurethane Prepolymer；By performed polymer stir speed (S.S.) be 2500r/
The emulsified 20min of min, 1.8g EDA are added after first adding 128.7g deionized waters immediately, make remaining-NCO reactions in emulsion
Completely.Butanone is evaporated off in 40 DEG C of backspins in emulsion, terminal hydroxy liquid modified rubber aqueous polyurethane matting resin emulsion is obtained.
Take appropriate emulsion casting film-forming in Teflon mould plate, drying at room temperature 7d dries 24h at 70 DEG C, obtains terminal hydroxy group liquid
Body rubber modified aqueous polyurethane matting resin glued membrane.
Embodiment 6
In equipped with agitator, reflux condensing tube, the reactor of thermometer add vaccum dewatering after 14.0g PHNA and
3.5g HTPI, add 18.8g IPDI and 0.01g catalyst DBTDL reactions 2h in 85 DEG C under nitrogen protection；It is cooled to 55 DEG C
1.5g DMPA and appropriate solvent butanone are added, 85 DEG C of reaction 3h are warming up to；Add after 1.3g BDO reactions 1h, cool to room
Temperature adds 1.1g TEA neutralization reaction 30min, obtains Waterborne Polyurethane Prepolymer；By performed polymer stir speed (S.S.) be 2500r/
The emulsified 20min of min, 2.7g EDA are added after first adding 128.7g deionized waters immediately, make remaining-NCO reactions in emulsion
Completely.Butanone is evaporated off in 40 DEG C of backspins in emulsion, terminal hydroxy liquid modified rubber aqueous polyurethane matting resin emulsion is obtained.
Take appropriate emulsion casting film-forming in Teflon mould plate, drying at room temperature 7d dries 24h at 70 DEG C, obtains terminal hydroxy group liquid
Body rubber modified aqueous polyurethane matting resin glued membrane.
Comparative example
The 22.4gPTMG added in equipped with agitator, reflux condensing tube, the reactor of thermometer after vaccum dewatering,
14.7g IPDI and 0.01g catalyst DBTDL reactions 2h is added under nitrogen protection in 80 DEG C；It is cooled to 60 DEG C of addition 1.5g
DMPA and appropriate solvent butanone, are warming up to 80 DEG C of reaction 3h；Add after 1.3g BDO reactions 1h, cool to room temperature and add 1.1g
TEA neutralization reaction 30min, obtain Waterborne Polyurethane Prepolymer；Performed polymer is emulsified for 2500r/min in stir speed (S.S.)
20min, 1.9g EDA are added after first adding 128.7g deionized waters immediately, make remaining-NCO reactions in emulsion complete.By breast
Butanone is evaporated off in 40 DEG C of backspins in liquid, obtains unmodified aqueous polyurethane emulsion.Appropriate emulsion is taken in Teflon mould plate
Middle casting film-forming, drying at room temperature 7d dries 24h at 70 DEG C, obtains unmodified aqueous polyurethane glued membrane.
The aqueous polyurethane matting resin obtained in above-described embodiment 1~6 and comparative example is tested below, emulsion grain
Footpath is tested using laser particle analyzer, and glossiness is using 60 ° of photometer tests, and water absorption rate is according to S=(m1-m0)/m0× 100% (m0
For the quality before water suction, m1For the quality after water suction) calculate, test result is as shown in the table：
| Numbering | Emulsion state | Particle diameter | 60 ° of glossiness | Water absorption rate |
| Embodiment 1 | A small amount of precipitation, it is redispersible | 127.5 | 8.1 | 14.4 |
| Embodiment 2 | A small amount of precipitation, it is redispersible | 146.3 | 5.4 | 5.4 |
| Embodiment 3 | A small amount of precipitation, it is redispersible | 161.3 | 9.5 | 4.8 |
| Embodiment 4 | A small amount of precipitation, it is redispersible | 85.6 | 5.5 | 6.0 |
| Embodiment 5 | A small amount of precipitation, it is redispersible | 113.7 | 8.8 | 5.7 |
| Embodiment 6 | A small amount of precipitation, it is redispersible | 177.0 | 2.6 | 3.7 |
| Comparative example | It is stable | 62.5 | 83.3 | 47.8 |
From upper table data, compared with comparative example, the aqueous poly- ammonia of terminal hydroxy liquid modified rubber prepared by the present invention
60 ° of glossiness of ester matting resin glued membrane are minimum up to 2.6 below 10, with good extinction effect；Meanwhile, water suction
Rate is significantly reduced, and glued membrane has excellent water resistance.Compared with prior art, preparation technology of the present invention is simple, safety and environmental protection, into
This is relatively low, with higher industrial application value.
Above-described to specifically describe, purpose, technical scheme and beneficial effect to invention have been carried out further specifically
It is bright, it should be understood that the specific embodiment that the foregoing is only the present invention, the protection model being not intended to limit the present invention
Enclose, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc. should be included in the present invention
Protection domain within.
Claims (10)
1. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin, it is characterised in that：Pass through the side of copolymerization
Terminal hydroxy liquid rubber is introduced into aqueous polyurethane system by formula, and longer non-polar carbon chains make in terminal hydroxy liquid rubber structure
In film forming procedure in hard section and soft segment microcell obvious microphase-separated can occur for emulsion, so that aqueous polyurethane glued membrane produces table
Face is coarse, realizes the purpose of delustring.
2. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin, it is characterised in that：Comprise the following steps that：
Step 1: the terminal hydroxy liquid rubber and polyether Glycols after vaccum dewatering or polyester diol are mixed, in inertia
Diisocyanate is added under gas shielded and mechanical agitation, is reacted under catalyst action to the content of remaining isocyano and reaches reason
By obtaining product A after value a；The quality of terminal hydroxy liquid rubber account for polyether Glycols or polyester diol quality 10~
50%；
Step 2: hydrophilic chain extender is added in the product A that step one is obtained, continue to react to the content of remaining isocyano
Reach after theoretical value b, obtain product B；The quality of hydrophilic chain extender accounts for the 3~10% of performed polymer gross mass；
Step 3: small molecule chain extender is added in the product B that step 2 is obtained, continue to react containing to remaining isocyano
Amount is reached after theoretical value c, obtains product C；The quality of small molecule chain extender accounts for the 1~3% of performed polymer gross mass；It is pre- to define R
In aggressiveness isocyano with Step 1: in step 2 and step 3 the material of all hydroxyls amount ratio, then need R ＞ 1；
Step 4: product C is down into room temperature, salt forming agent is then added, until the neutralization reaction of salt forming agent and hydrophilic chain extender is complete
Entirely, performed polymer is obtained；The amount ratio of the material of salt forming agent and hydrophilic chain extender is 1:1；
Step 5: the performed polymer obtained by step 4 is scattered emulsified in high speed, emulsification adds rear chain extender immediately after starting, and obtains
To terminal hydroxy liquid modified rubber aqueous polyurethane matting resin；Amido and remaining isocyano in performed polymer in rear chain extender
The amount ratio of material is 1:1；
Step 1: the calculation formula of the isocyano theoretical value described in two, three is respectively：
<mrow>
<mi>a</mi>
<mo>=</mo>
<mfrac>
<mrow>
<mo>&lsqb;</mo>
<mi>n</mi>
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<mi>N</mi>
<mi>C</mi>
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<msub>
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<mn>1</mn>
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<mi>n</mi>
<mn>2</mn>
</msub>
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<mo>(</mo>
<mi>O</mi>
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<mo>)</mo>
</mrow>
<mo>&rsqb;</mo>
<mo>&times;</mo>
<mi>M</mi>
<mrow>
<mo>(</mo>
<mi>N</mi>
<mi>C</mi>
<mi>O</mi>
<mo>)</mo>
</mrow>
</mrow>
<mi>m</mi>
</mfrac>
<mo>&times;</mo>
<mn>100</mn>
<mi>%</mi>
<mo>;</mo>
</mrow>
<mrow>
<mi>b</mi>
<mo>=</mo>
<mfrac>
<mrow>
<mo>&lsqb;</mo>
<mi>n</mi>
<mrow>
<mo>(</mo>
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<mi>C</mi>
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<mo>)</mo>
</mrow>
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<mn>1</mn>
</msub>
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<mo>(</mo>
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<mo>)</mo>
</mrow>
<mo>-</mo>
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<mi>n</mi>
<mn>2</mn>
</msub>
<mrow>
<mo>(</mo>
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</mrow>
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<msub>
<mi>n</mi>
<mn>3</mn>
</msub>
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<mi>O</mi>
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<mo>)</mo>
</mrow>
<mo>&rsqb;</mo>
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<mi>M</mi>
<mrow>
<mo>(</mo>
<mi>N</mi>
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<mi>O</mi>
<mo>)</mo>
</mrow>
</mrow>
<mi>m</mi>
</mfrac>
<mo>&times;</mo>
<mn>100</mn>
<mi>%</mi>
<mo>;</mo>
</mrow>
<mrow>
<mi>c</mi>
<mo>=</mo>
<mfrac>
<mrow>
<mo>&lsqb;</mo>
<mi>n</mi>
<mrow>
<mo>(</mo>
<mi>N</mi>
<mi>C</mi>
<mi>O</mi>
<mo>)</mo>
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<msub>
<mi>n</mi>
<mn>1</mn>
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<mo>(</mo>
<mi>O</mi>
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<mo>)</mo>
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<mn>2</mn>
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<msub>
<mi>n</mi>
<mn>4</mn>
</msub>
<mrow>
<mo>(</mo>
<mi>O</mi>
<mi>H</mi>
<mo>)</mo>
</mrow>
<mo>&rsqb;</mo>
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<mi>M</mi>
<mrow>
<mo>(</mo>
<mi>N</mi>
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<mo>)</mo>
</mrow>
</mrow>
<mi>m</mi>
</mfrac>
<mo>&times;</mo>
<mn>100</mn>
<mi>%</mi>
<mo>;</mo>
</mrow>
Wherein n(NCO)The amount of the material of isocyano in=diisocyanate；n1(OH) thing of hydroxyl in=terminal hydroxy liquid rubber
The amount of matter；n2(OH) amount of the material of hydroxyl in=polyether Glycols or polyester diol；n3(OH) hydroxyl in=hydrophilic chain extender
Material amount；n4(OH) amount of the material of hydroxyl in=chain extender；M(NCO)The molal weight of=isocyano, is fixed value
42g/mol；The gross mass of m=performed polymers.
3. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Terminal hydroxy liquid rubber described in step one includes end hydroxy butadiene and hydroxyl terminated polyisoprene.
4. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Polyether Glycols described in step one or polyester diol include PTMG, polyadipate ethylene glycol the third two
Alcohol ester or polyadipate ethylene glycol DOPCP；Diisocyanate described in step one include isoflurane chalcone diisocyanate,
Toluene di-isocyanate(TDI), 1,6- hexyl diisocyanates, methyl diphenylene diisocyanate or the isocyanic acid of tetramethyl-ring hexyl two
Ester.
5. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Catalyst described in step one includes dibutyl tin laurate, tert-butyl group tin or organic bismuth catalyst.
6. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Hydrophilic chain extender described in step 2 includes dihydromethyl propionic acid or 2,2- dimethylolpropionic acids.
7. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Small molecule chain extender described in step 3 includes 1,4- butanediols or 1,6-HD.
8. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Salt forming agent described in step 4 includes triethylamine or tri-n-butylamine.
9. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Rear chain extender described in step 5 includes ethylenediamine, 1,6- hexamethylene diamines or hydrazine hydrate.
10. a kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin as claimed in claim 2, its feature
It is：Temperature when adding diisocyanate described in step one is 70~90 DEG C；Step one obtains first cooling after product A 20~
Hydrophilic chain extender is added after 30 DEG C, 70~90 DEG C of reactions are then warming up to；The step 3, which is maintained at 70~90 DEG C, reacts.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111891A (en) * | 2018-07-03 | 2019-01-01 | 南京理工大学 | HTPB modified aqueous polyurethane transfer adhesive and preparation method thereof |
| CN110240688A (en) * | 2019-05-24 | 2019-09-17 | 合肥科天水性科技有限责任公司 | Agent waterborne polyurethane resin and preparation method thereof at a kind of table |
| CN111423558A (en) * | 2020-05-26 | 2020-07-17 | 福建华夏蓝新材料科技有限公司 | Preparation method of self-extinction aqueous polyurethane dispersion |
| CN111647132A (en) * | 2020-06-09 | 2020-09-11 | 上海华峰超纤科技股份有限公司 | Preparation method and application of low-elasticity polyurethane resin |
| CN114395104A (en) * | 2021-12-27 | 2022-04-26 | 湖北三棵树新材料科技有限公司 | Preparation method of self-extinction aqueous polyurethane emulsion |
| CN115947947A (en) * | 2022-12-26 | 2023-04-11 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
| CN116656229A (en) * | 2023-04-18 | 2023-08-29 | 淮阴工学院 | Preparation method of stain-resistant modified waterborne polyurethane coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977320A (en) * | 2012-11-12 | 2013-03-20 | 青岛文创科技有限公司 | Method for modifying water-based polyurethane by using hydroxyl terminated polybutadiene |
| CN103193954A (en) * | 2013-04-02 | 2013-07-10 | 上海水贝司化工有限公司 | Preparation method of aqueous polyurethane dispersion and application of aqueous polyurethane dispersion |
| CN105062347A (en) * | 2015-07-16 | 2015-11-18 | 合肥市科天化工有限公司 | Synthetic method for matte waterborne polyurethane resin composite emulsion |
-
2017
- 2017-07-04 CN CN201710536904.XA patent/CN107141442A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977320A (en) * | 2012-11-12 | 2013-03-20 | 青岛文创科技有限公司 | Method for modifying water-based polyurethane by using hydroxyl terminated polybutadiene |
| CN103193954A (en) * | 2013-04-02 | 2013-07-10 | 上海水贝司化工有限公司 | Preparation method of aqueous polyurethane dispersion and application of aqueous polyurethane dispersion |
| CN105062347A (en) * | 2015-07-16 | 2015-11-18 | 合肥市科天化工有限公司 | Synthetic method for matte waterborne polyurethane resin composite emulsion |
Non-Patent Citations (2)
| Title |
|---|
| 许戈文等: "《水性聚氨酯材料》", 28 February 2007, 化学工业出版社 * |
| 赵孝彬等: "聚氨酯的结构与微相分离", 《聚氨酯工业》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111891A (en) * | 2018-07-03 | 2019-01-01 | 南京理工大学 | HTPB modified aqueous polyurethane transfer adhesive and preparation method thereof |
| CN109111891B (en) * | 2018-07-03 | 2020-12-25 | 南京理工大学 | HTPB (high temperature polybutadiene) modified waterborne polyurethane transfer adhesive and preparation method thereof |
| CN110240688A (en) * | 2019-05-24 | 2019-09-17 | 合肥科天水性科技有限责任公司 | Agent waterborne polyurethane resin and preparation method thereof at a kind of table |
| CN111423558A (en) * | 2020-05-26 | 2020-07-17 | 福建华夏蓝新材料科技有限公司 | Preparation method of self-extinction aqueous polyurethane dispersion |
| CN111647132A (en) * | 2020-06-09 | 2020-09-11 | 上海华峰超纤科技股份有限公司 | Preparation method and application of low-elasticity polyurethane resin |
| CN111647132B (en) * | 2020-06-09 | 2022-01-07 | 上海华峰超纤科技股份有限公司 | Preparation method and application of low-elasticity polyurethane resin |
| CN114395104A (en) * | 2021-12-27 | 2022-04-26 | 湖北三棵树新材料科技有限公司 | Preparation method of self-extinction aqueous polyurethane emulsion |
| CN115947947A (en) * | 2022-12-26 | 2023-04-11 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
| CN115947947B (en) * | 2022-12-26 | 2023-10-31 | 浙江震东新材料有限公司 | Functional finishing agent copolymer and preparation method thereof |
| CN116656229A (en) * | 2023-04-18 | 2023-08-29 | 淮阴工学院 | Preparation method of stain-resistant modified waterborne polyurethane coating |
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