CN106188478A - A kind of modified polyurethane emulsion film former and its preparation method and application - Google Patents
A kind of modified polyurethane emulsion film former and its preparation method and application Download PDFInfo
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- CN106188478A CN106188478A CN201610605604.8A CN201610605604A CN106188478A CN 106188478 A CN106188478 A CN 106188478A CN 201610605604 A CN201610605604 A CN 201610605604A CN 106188478 A CN106188478 A CN 106188478A
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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
- C08G18/70—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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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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
- C08G18/08—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/42—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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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a kind of modified polyurethane emulsion film former and its preparation method and application, wherein, this film former includes that following components, the percentage by weight of each component are expressed as follows: PEPA 55～65%, unsaturated dibasic acid 1～5%, diisocyanate 20～40%, chain extender 1.5～10%, salt forming agent 0.1～5%, organotin catalysts 0.05～0.2%.Aqueous polyurethane emulsion is modified by this film former by unsaturated dibasic acid, this modified polyurethane emulsion film former is used to prepare wetting agent, and then apply it in the preparation of FRP goods, can preferably make up the part interface caused at fiberglass surfacing skewness because of coupling agent and combine unstable defect, so that FRP composite has more preferable mechanical property.
Description
Technical field
The present invention relates to a kind of modified polyurethane emulsion film former and its preparation method and application, be specifically related to use insatiable hunger
With binary acid modified aqueous polyurethane emulsion film former and preparation method thereof, apply glass fiber industry.
Background technology
Polyurethane resin function admirable, of many uses, it is applied to traffic, transport, clothing, weaving, synthetic leather etc. many
Field.Glass fibre is a kind of reinforcing material, has high intensity, low stretching contracting, corrosion-resistant, electric insulation, the excellence such as nonflammable
Performance, but its property is crisp, the most wear-resisting, easy static electrification after friction, and smooth surface, be difficult to when doing the reinforcing material of resin with
Resin-bonded, it is therefore necessary to glass fibre film former to just processing from wire-drawing process glass fibre out.
Film former is a kind of waterborne polymeric diluent, is typically used in mixed way with coupling agent and other auxiliary agent.Through film forming
After agent processes, fiberglass surfacing is coated with film substrate, and the processing characteristics of glass fibre is very significantly improved, and energy
Enough adhesive effects stronger with being enhanced resin generation.The effect of film-forming resin is thicker and tough and tensile fiber surface formation one layer
Continuous protecting film, prevent fiber by frictionally damage, the continuous protecting film that simultaneously formed is it is necessary to have good elasticity, with suitable
Answer high-speed wire-drawing technique.Aqueous polyurethane is as a branch of polyurethane resin, superior performance, and after film forming, intensity is high, toughness,
Good springiness.Being applied to glass fibre process, its adhesive property and filming performance are the most excellent, as long as adding few in film former formula
The polyaminoester emulsion of amount, can be effectively improved the convergence of glass fiber yarn, choppability and wearability, can effectively protect glass fibers
Dimension, polarity is strong simultaneously, is well combined with most matrix resin, is aided with High Efficient Bonding Agents, can preferably solve interface cohesion
Problem, and the part interface caused at fiberglass surfacing skewness because of coupling agent combines unstable defect.
Summary of the invention
It is an object of the invention to provide a kind of modified polyurethane emulsion film former and preparation method thereof, by unsaturated binary
Aqueous polyurethane emulsion is modified by acid, uses this modified polyurethane emulsion film former to prepare wetting agent, and then is applied
In the preparation of FRP goods, can preferably make up part circle caused because of coupling agent at fiberglass surfacing skewness
Face combines unstable defect, so that FRTP composite has more preferable mechanical property.
The present invention provides a kind of modified polyurethane emulsion film former, including following components, the percentage by weight table of each component
Show as follows:
Wherein, including following components, the percentage by weight of each component is expressed as follows:
Wherein, including following components, the percentage by weight of each component is expressed as follows:
Wherein, described PEPA is polyadipate-BDO, polyadipate ethylene glycol, polyadipate one contracting
At least one in diethylene glycol, polyadipate neopentyl glycol.
Wherein, described PEPA is polyadipate neopentyl glycol.
Wherein, described diisocyanate is isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate
(HDI), at least one in toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI).
Wherein, described diisocyanate is isoflurane chalcone diisocyanate (IPDI).
Wherein, described chain extender includes that hydrophilic chain extender and diamine chain extenders, described hydrophilic chain extender are dihydroxymethyl
Propanoic acid (DMPA), described diamine chain extenders is ethylenediamine (EDA), wherein, described hydrophilic chain extender and described diamine chain extension
The weight ratio of agent is 3.5:1～4.5:1；
Described unsaturated dibasic acid is cis-butenedioic anhydride (maleic anhydride), fumaroyl (fumaric acid), glutaconate, hexadiene
At least one in diacid；
Described salt forming agent is triethylamine (TEA)；
Described organotin catalysts is dibutyl tin dilaurate or stannous octoate.
The present invention also provides for the preparation method of a kind of film former, comprises the following steps:
1S: unsaturated dibasic acid and PEPA are carried out esterification, forms the polyester containing unsaturated double-bond many
Unit's alcohol；
2S: by anti-to the PEPA containing unsaturated double-bond and diisocyanate, hydrophilic chain extender, organotin catalysts
Should, it is subsequently adding acetone solution, generates performed polymer；
3S: performed polymer is poured into Scattered Kettle, in whipping process, adds salt forming agent and deionized water carries out emulsifying, in emulsifying
During add ethylenediamine chain extender and carry out chain extension, again add deionized water, stir 20-30min, emulsion evacuation is removed
Acetone obtains modified polyurethane emulsion film former.
The present invention also provides for above-mentioned film former purposes on glass fibre produces.
The modified polyurethane emulsion film former provided according to the present invention, including PEPA, unsaturated dibasic acid, two different
Cyanate, chain extender, salt forming agent and organotin catalysts.
PEPA and diisocyanate are the primary raw material preparing polyaminoester emulsion, and both carry out catalytic polymerization,
Accounting for major portion in film former, percentage by weight is respectively PEPA 55～65%；Diisocyanate 20～40%；Preferably
, PEPA 56～63%；Diisocyanate 25～35%；It is further preferred that PEPA 57～62%；Two is different
Cyanate 27～32%.
Unsaturated dibasic acid is cis-butenedioic anhydride (maleic anhydride), fumaroyl (fumaric acid), glutaconate, muconic acid
In at least one.Introducing the purpose of unsaturated dibasic acid: first, it has the more preferable compatibility with FRP unsaturated polyester resin,
The wetting velocity of glass fibre can be improved；Secondly, unsaturated double-bond reacts with the unsaturated double-bond of resin, improves resin
Adhesion with glass fibre.In order to obtain the insatiable hunger of terminal hydroxy group after ensureing unsaturated dibasic acid and polyester diol esterification
And polyester diol, unsaturated dibasic acid ratio in this film former is 1～5%, it is preferred that 1～3.5%, the most excellent
Choosing, 1.4～3%.
Chain extender includes two kinds, respectively hydrophilic chain extender and diamine chain extenders, and the effect of hydrophilic chain extender mainly carries
Supply hydrophilic group and chain extension to increase molecular weight.It is the best that hydrophilic chain extender added emulsifiability at least, and emulsion can be caused unstable
Fixed；Added resistance to water at most to reduce.Diamine chain extenders is mainly chain extension, increases molecular weight, general diamine chain extenders
Amount is 70% (mole) of residue NCO.The percentage by weight of chain extender is 1.5～10%, it is preferred that 3～7%, the most excellent
Choosing, 3.5～6%.Wherein, hydrophilic chain extender is 3.5:1～4.5:1 with the weight ratio of diamine chain extenders.
Salt forming agent is triethylamine, and weight ratio shared in film former is 0.1～5%, it is preferred that 1～3%, further
Preferably, 2.5-2.8%.Salt forming agent is to neutralize the carboxyl in hydrophilic chain extender, thus generates the more preferable salt of hydrophilicity, becomes salt
The amount of agent and hydrophilic chain extender mol ratio are 1:1.
The present invention compared with prior art, in the preparation process of polyaminoester emulsion, adds unsaturated dibasic acid to poly-ammonia
Ester emulsion is modified, and prepared modified polyurethane emulsion film former is prepared as wetting agent, and then is applied to FRP goods
In preparation, can preferably make up the part interface caused at fiberglass surfacing skewness because of coupling agent and combine insecure
Defect so that FRTP composite has more preferable mechanical property.
The each component of film former of the present invention and the selection of content thereof, film former the beneficial effect of preparation method will be by real
Execute example to provide specific experiment data and illustrate.
Accompanying drawing explanation
The accompanying drawing of the part being incorporated in description and constitute description shows embodiments of the invention, and with
Describing together for explaining the principle of the present invention, in the drawings, similar reference is used for representing similar key element, under
Accompanying drawing during face describes is some embodiments of the present invention rather than whole embodiment, comes for those of ordinary skill in the art
Say, on the premise of not paying creative work, other accompanying drawing can be obtained according to these accompanying drawings.
Fig. 1 shows the preparation flow figure of a kind of film former according to the present invention.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
The a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under not making creative work premise, broadly falls into the scope of protection of the invention.Need
Illustrating, in the case of not conflicting, the embodiment in the application and the feature in embodiment can mutual combination in any.
The modified polyurethane emulsion film former of the present invention includes that following components, the percentage by weight of each component are expressed as follows:
PEPA 55～65%；Unsaturated dibasic acid 1～5%；Diisocyanate 20～40%；Chain extender 1.5～10%；Become salt
Agent 0.1～5%；Organotin catalysts 0.05～0.2%.
Preferably, PEPA 56～63%；Unsaturated dibasic acid 1～3.5%；Diisocyanate 25～35%；Expand
Chain agent 3～7%；Salt forming agent 1～3%；Organotin catalysts 0.05～0.1%.
It is further preferred that PEPA 57～62%；Unsaturated dibasic acid 1.4～3%；Diisocyanate 27～
32%；Chain extender 3.5～6%；Salt forming agent 2.5-2.8%；Organotin catalysts 0.05～0.1%.
The preparation method of this film former comprises the following steps:
1S: unsaturated dibasic acid and PEPA are carried out esterification, forms the polyester containing unsaturated double-bond many
Unit's alcohol；
2S: by anti-to the PEPA containing unsaturated double-bond and diisocyanate, hydrophilic chain extender, organotin catalysts
Should, it is subsequently adding acetone solution, generates performed polymer；
3S: performed polymer is poured into Scattered Kettle, in whipping process, adds salt forming agent and deionized water carries out emulsifying, in emulsifying
During add ethylenediamine chain extender and carry out chain extension, again add deionized water, stir 20-30min, emulsion evacuation is removed
Acetone obtains modified polyurethane emulsion film former.
The specific embodiment of this film former component and preparation method is given below.
Embodiment 1
In the present embodiment, each component of film former and percentage by weight:
Preparation process is:
1S: put into cis-butenedioic anhydride 9.6g and polyadipate neopentyl glycol 200g in four-hole boiling flask, be progressively warming up to 180 DEG C of reactions
After 2 hours, evacuation dehydration is down to less than 3 when acid number, is cooled to 70 DEG C；
2S: adding IPDI 90g, DMPA 18g, dibutyl tin dilaurate 4,60～70 DEG C of reaction to-NCO concentration reach
150g acetone solution is added after theoretical value；
3S: poured into by performed polymer in Scattered Kettle, is cooled to 35 DEG C, and high-speed stirred (3000r/min) adds triethylamine 9.5g,
Add deionized water 500g, add ethylenediamine 3.96g, high-speed stirred 20～30min.Take off at 50～60 DEG C of low pressure evacuation
Aqueous polyurethane emulsion is obtained after acetone.
Wherein ,-NCO concentration monitor the method in step be by di-n-butylamine method monitoring system-change of NCO content.
The embodiment table data of this film former formula being given below including embodiment 1.
Table 1 film former specific embodiment list
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Poly-adipic acid neopentyl glycol | 60.38% | 59.77% | 58.79% | 58.24% | 57.87% |
| Unsaturated dibasic acid | 2.90% | 2.39% | 2.06% | 1.75% | 1.45% |
| IPDI | 27.17% | 28.39% | 29.69% | 30.57% | 31.24% |
| DMPA | 5.42% | 5.33% | 5.24% | 5.24% | 5.2% |
| TEA | 2.86% | 2.8% | 2.79% | 2.67% | 2.7% |
| EDA | 1.21% | 1.23% | 1.38% | 1.43% | 1.48% |
| Dibutyl tin dilaurate | 0.06% | 0.09% | 0.05% | 0.1% | 0.06% |
It should be noted that the unsaturated dibasic acid used in embodiment 1-3 is cis-butenedioic anhydride, institute in embodiment 4,5
The unsaturated dibasic acid used is fumaric acid.
Contrast test example
In order to further illustrate beneficial effects of the present invention, we are using above-mentioned homemade anion aqueous polyurethane as master
Film former, is applied in the chopped roving sizing agent formula (import aqueous polyurethane is as main film former) of maturation carry out application real
Testing, wetting agent formula is as follows:
The wetting agent using our homemade anion aqueous polyurethane to be main film former and use import aqueous polyurethane
It is that the application of the wetting agent A of main film former contrasts.Wherein, the mechanic property test method of prepared FRP is according to GB/
T15232-1994 is measured.Concrete comparing result is listed as follows:
The performance test results of the different FRP goods of table 2
It should be noted that the FRP goods of embodiment 1-5 in table 2 corresponding be the modification of embodiment 1-5 in table 1
The formula of polyurethane finishing agent.
From above-mentioned test case it will be seen that use the infiltration that the film former of present invention offer is prepared as main film former
Agent is applied in FRP goods, and wetting-out rate is fast, hot strength, bending strength, bending modulus and unnotched impact strength all than
Comparative example wetting agent A is significantly improved.
In sum, aqueous polyurethane emulsion is modified by the present invention by unsaturated dibasic acid, uses this modification to gather
Urethane emulsion film forming agent prepares wetting agent, and then applies it in the preparation of FRP goods, can preferably make up because coupling agent exists
Fiberglass surfacing skewness and the part interface that causes combines unstable defect, so that FRTP composite has
Preferably mechanical property.
Last it is noted that the most in this article, term " includes ", " comprising " or its any other variant are intended to non-
Comprising of exclusiveness, so that comprise the process of a series of key element, method, article or equipment not only include those key elements,
But also include other key elements being not expressly set out, or also include being consolidated by this process, method, article or equipment
Some key elements.In the case of there is no more restriction, statement " including ... " key element limited, it is not excluded that including
State and the process of key element, method, article or equipment there is also other identical element.
Above example only in order to technical scheme to be described, is not intended to limit.Although with reference to previous embodiment
The present invention is described in detail, it will be understood by those within the art that: it still can be to aforementioned each enforcement
Technical scheme described in example is modified, or wherein portion of techniques feature is carried out equivalent；And these amendment or
Replace, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a modified polyurethane emulsion film former, it is characterised in that include that following components, the percentage by weight of each component represent
As follows:
2. modified polyurethane emulsion film former as claimed in claim 1, it is characterised in that include following components, each component
Percentage by weight is expressed as follows:
3. modified polyurethane emulsion film former as claimed in claim 1, it is characterised in that include following components, each component
Percentage by weight is expressed as follows:
4. the modified polyurethane emulsion film former as according to any one of claim 1-3, it is characterised in that described polyester polyols
Alcohol is polyadipate-1,4-butanediol, polyadipate ethylene glycol, polyadipate diglycol, polyadipate neopentyl glycol
In at least one.
5. modified polyurethane emulsion film former as claimed in claim 4, it is characterised in that described PEPA for poly-oneself two
Acid neopentyl glycol.
6. the modified polyurethane emulsion film former as according to any one of claim 1-3, it is characterised in that described two Carbimide .s
Ester is isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene di-isocyanate(TDI) (TDI), hexichol
At least one in dicyclohexylmethane diisocyanate (MDI).
7. modified polyurethane emulsion film former as claimed in claim 6, it is characterised in that described diisocyanate is different fluorine that
Ketone diisocyanate (IPDI).
8. the modified polyurethane emulsion film former as according to any one of claim 1-3, it is characterised in that described chain extender bag
Including hydrophilic chain extender and diamine chain extenders, described hydrophilic chain extender is dihydromethyl propionic acid (DMPA), described diamine chain extension
Agent is ethylenediamine (EDA), and wherein, described hydrophilic chain extender is 3.5:1～4.5:1 with the weight ratio of described diamine chain extenders；
Described unsaturated dibasic acid is cis-butenedioic anhydride (maleic anhydride), fumaroyl (fumaric acid), glutaconate, muconic acid
In at least one；
Described salt forming agent is triethylamine (TEA)；
Described organotin catalysts is dibutyl tin dilaurate or stannous octoate.
9. according to a preparation method for the modified polyurethane emulsion film former according to any one of claim 1-8, its feature
Being, described preparation method comprises the following steps:
1S: unsaturated dibasic acid and PEPA are carried out esterification, forms the PEPA containing unsaturated double-bond；
2S: the PEPA containing unsaturated double-bond is reacted with diisocyanate, hydrophilic chain extender, organotin catalysts,
It is subsequently adding acetone solution, generates performed polymer；
3S: performed polymer is poured into Scattered Kettle, in whipping process, adds salt forming agent and deionized water carries out emulsifying, in emulsion process
Middle addition ethylenediamine chain extender carries out chain extension, again adds deionized water, stirs 20-30min, and emulsion evacuation is removed acetone
Obtain modified polyurethane emulsion film former.
10. the modified polyurethane emulsion film former as according to any one of claim 1-8 is on glass fibre produces
Purposes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868204A (en) * | 2017-11-30 | 2018-04-03 | 上海大学 | Anionic water type polyurethane resin, its preparation method and its application |
| CN108484891A (en) * | 2018-03-12 | 2018-09-04 | 吉林乾仁新材料有限公司 | The preparation of self assembly self-emulsifying self-stabilization polyester-type high-performance fiber interface modification auxiliary agent and product and application |
| CN110079206A (en) * | 2019-05-08 | 2019-08-02 | 珠海长先新材料科技股份有限公司 | A kind of aqueous polyurethane three-proofing coating and preparation method thereof |
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| CN115505326A (en) * | 2022-11-16 | 2022-12-23 | 山东一诺威聚氨酯股份有限公司 | Dual-curing polyurethane floor coating and preparation method thereof |
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