CN106832139B - Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer - Google Patents

Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer Download PDF

Info

Publication number
CN106832139B
CN106832139B CN201710038048.5A CN201710038048A CN106832139B CN 106832139 B CN106832139 B CN 106832139B CN 201710038048 A CN201710038048 A CN 201710038048A CN 106832139 B CN106832139 B CN 106832139B
Authority
CN
China
Prior art keywords
polyurethane
copolymer
carboxy copolymer
latex
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710038048.5A
Other languages
Chinese (zh)
Other versions
CN106832139A (en
Inventor
江一明
陈卓雄
蔡辉
董巍
伍云俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinhui (china) New Material Co Ltd
Original Assignee
Xinhui (china) New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinhui (china) New Material Co Ltd filed Critical Xinhui (china) New Material Co Ltd
Priority to CN201710038048.5A priority Critical patent/CN106832139B/en
Publication of CN106832139A publication Critical patent/CN106832139A/en
Priority to PCT/CN2017/117257 priority patent/WO2018133610A1/en
Application granted granted Critical
Publication of CN106832139B publication Critical patent/CN106832139B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/667—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
    • C08G18/6685—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 C08G18/3225 or polyamines of C08G18/38
    • 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
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
    • C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • 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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

The present invention relates to a kind of latex comprising polyurethane-modified Carboxy copolymer, wherein polyurethane and Carboxy copolymer are keyed via covalent in the polyurethane-modified Carboxy copolymer, and the polyurethane includes hydrophilic group.The present invention also provides a kind of methods for preparing the latex.Of the invention includes the advantages of latex of polyurethane-modified Carboxy copolymer has had both both carboxylic styrene butadiene latex and polyurethane rubber latex, is had excellent performance, and can be used as adhesive for carpet manufacture, building, papermaking, leather, textile printing and dyeing and cement.

Description

Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer
Technical field
The present invention relates to a kind of latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer.The present invention is also It is related to the latex in carpet manufacture, building, papermaking, leather, textile printing and dyeing and cement as the purposes of adhesive.
Technical background
Carpet is a kind of special fabric, needs to carry out backside coating with adhesive in production process, main function is not Tufting and anchoring fiber backing are only anchored, and assigns carpet with feel, plays stable dimensions, waterproof, wear-resisting, raising by force The effect of degree and service life.For decades, carpet backing glue is also from earliest Heveatex gradually till now with butylbenzene Synthetic latex based on latex, especially carboxylic styrene butadiene latex become the main product of Carpet Adhesive with its excellent cost performance.
Styrene-butadiene latex is to be made by butadiene and styrene by emulsion polymerization, is the relatively early rubber polymer for being used as Carpet Adhesive Cream.Later it has been found that being introduced into unsaturated acid monomer as third component in copolymerization of butylbenzene system, gained carboxy styrene-butadiene rubber Cream can significantly improve latex to the adhesive strength of carpet fabric；In addition carboxy styrene-butadiene rubber dairy milk starting material is easy to get, and small investment is produced into This is lower, thus has captured Carpet Adhesive market quickly.About the synthetic method of carboxylic styrene butadiene latex, in many patents and document It has been reported that, such as US4876293, US5726259, CN87105487A, CN103755872A.It has however been found that carboxylic styrene butadiene latex is raw The carpet of production compares shortcoming in terms of wet peel strength, freedom from cracking and feel, is not able to satisfy the requirement of high-grade carpet.
Polyurethane rubber latex has many advantages, such as that adhesive strength is high, low temperature resistant, wear-resisting, performance is adjustable, coating, adhesive, The fields such as textile finishing, leather finish, automobile coating are widely applied.It is many special about the synthetic method of polyurethane rubber latex Has play-by-play in benefit and document, for example, see US 5221710, CN 201410139090.2.CN 1250497A is described Polyurethane rubber latex prepares Carpet Adhesive as adhesive.Although polyurethane rubber latex can satisfy advanced carpet and want to comprehensive performance It asks, but expensive compared with carboxylic styrene butadiene latex, it is difficult to be used widely in carpet industry.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly, will as a result, it has been found that working as When latex comprising polyurethane-modified Carboxy copolymer of the invention is used for carpet manufacture, gained carpet has good machine Tool stability, chemical stability, immersion dimensional stability, peel strength is high, suede cluster withdrawal force is high and ageing-resistant performance is good.This hair The bright latex comprising polyurethane-modified Carboxy copolymer has both carboxylic styrene butadiene latex and polyurethane rubber latex advantage, is a kind of New material with good cost performance.In addition, it has been found that the latex comprising polyurethane-modified Carboxy copolymer of the invention It can be prepared under conditions of emulsifier is not added less plus even.It is not added or adds emulsifier to can also be improved the water-fast of product less Property.It has furthermore been found that can cause if introducing the carbon-carbon double bond of a small amount of free redical polymerization in above-mentioned polyurethane molecular In the presence of agent, by radical polymerization mechanism by styrene, butadiene, unsaturated acids and other vinyl monomer copolymerizations to poly- ammonia On ester molecule chain, and polymerization process is stablized, and gained polyurethane-Carboxy copolymer latex stability is good, is easy to industrialization.
The present invention is based on the above discovery and is accomplished.
The object of the present invention is to provide it is a kind of have excellent performance, the synthetic latex that cost performance is high.It is used for when by latex of the present invention When in carpet manufacture, gained carpet has good mechanical stability, chemical stability, immersion dimensional stability, peel strength Height, suede cluster withdrawal force are high and ageing-resistant performance is good.
It is a further object of the present invention to provide a kind of methods for preparing the synthetic latex.
Realize that the technical solution of the object of the invention can be summarized as follows:
1. a kind of latex comprising polyurethane-modified Carboxy copolymer, wherein the polyurethane-modified Carboxy is total Polyurethane and Carboxy copolymer are via covalent key connection in polymers, and the polyurethane includes hydrophilic group.
2. according to the 1st latex comprising polyurethane-modified Carboxy copolymer, wherein described polyurethane-modified In Carboxy copolymer the weight ratio of polyurethane and Carboxy copolymer be 40:60-3:97, preferably 30:70-5:95, more It is preferred that 25:75-8:92；And/or the hydrophilic group on the polyurethane is selected from carboxyl, sulfonic group and its salt.
3. according to the 1st or 2 latex comprising polyurethane-modified Carboxy copolymer, wherein the polyurethane passes through So that polyalcohol and polyisocyanates is carried out sudden reaction, then further with the chain extender containing the hydrophilic group, another small molecule It is anti-that chain extender and monomer with the group and free redical polymerization carbon-carbon double bond that can be reacted with isocyanate group carry out addition polymerization It answers and prepares.
4. according to the 3rd latex comprising polyurethane-modified Carboxy copolymer, wherein the molecule of the polyalcohol Amount is 400-4000g/mol, preferably 600-3000g/mol；And/or wherein the polyalcohol is selected from hydroxyl value as 20-200mgKOH/ G, preferably 40-120mgKOH/g, the pure and mild polyether polyol of the polyester polyols of more preferable 50-100mgKOH/g.
5. according to the 3rd or 4 latex comprising polyurethane-modified Carboxy copolymer, wherein described includes hydrophilic group Chain extender be selected from 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid, 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium, 1,4- fourth two Alcohol -2- sodium sulfonate, second diamino ethanesulfonic acid sodium and second dihydroxy ethanesulfonic acid sodium.
6. according to any one of the 3-5 latex comprising polyurethane-modified Carboxy copolymer, wherein the tool Having the monomer of the group and free redical polymerization carbon-carbon double bond that can react with isocyanate group to be selected from has 1-10 carbon atom Glycol with the α of 3-10 carbon atom, the ester of the β-olefinic mono- and/or dicarboxylic acids of unsaturation and its acid anhydrides or with hydroxyl Acrylamide, preferably (methyl) acrylic acid C2-C6Hydroxyalkyl acrylate and N, the bis- (C of N-2-C6Hydroxyalkyl) acrylamide；And/or Wherein the amount of the monomer with the group and free redical polymerization carbon-carbon double bond that can react with isocyanate group is 0.1-5 weight %, preferably 0.2-2 weight %, more preferable 0.3-1 weight % are measured, with the sum of each component weight for being used to prepare polyurethane for base It is quasi-.
7. according to any one of the 1-6 latex comprising polyurethane-modified Carboxy copolymer, wherein the carboxylic It includes 1-15 weight %, preferably 1.5-12 weight %, more preferable 2-8 that base butylbenzene copolymer, which is based on the Carboxy copolymer weight, The monoethylenically unsaturated carboxylic acid monomeric unit of weight %；And/or wherein the monoethylenically unsaturated carboxylic acid is selected from containing being no more than The monoethylenically unsaturated carboxylic acid of 10 carbon atoms, the monoethylenically unsaturated carboxylic acid of preferably more than 6 carbon atoms.
8. a kind of latex prepared as defined in any one of 1-7 comprising polyurethane-modified Carboxy copolymer Method comprising
A) there is the polyurethane of free redical polymerization carbon-carbon double bond and hydrophilic group by sudden reaction preparation, and
B) in the presence of the polyurethane with free redical polymerization carbon-carbon double bond and hydrophilic group obtained by step a), pass through Emulsion polymerization prepares Carboxy copolymer, obtains the latex comprising polyurethane-modified Carboxy copolymer.
9. wherein the emulsion polymerization in step b) can be carried out in the case where being added without emulsifier according to the 8th method.
10. the latex as defined in any one of 1-7 comprising polyurethane-modified Carboxy copolymer is in carpet Purposes in production, building, papermaking, leather, textile printing and dyeing and cement as adhesive.
Specific embodiment
One aspect of the present invention is related to a kind of latex comprising polyurethane-modified Carboxy copolymer, wherein described poly- Polyurethane and Carboxy copolymer are keyed via covalent in urethane modified carboxyl butylbenzene copolymer, and the polyurethane packet Containing hydrophilic group.
In a preferred embodiment of the invention, in the polyurethane-modified Carboxy copolymer, polyurethane and The weight ratio of Carboxy copolymer is 40:60-3:97, preferably 30:70-5:95, more preferable 25:75-8:92.
According to the present invention, the hydrophilic group on the polyurethane can be selected from carboxyl, sulfonic group and its salt.
In a preferred embodiment of the invention, the polyurethane is by adding polyalcohol and polyisocyanates Poly- reaction, then further with chain extender, another small molecule chain extender and have can be with isocyanates containing the hydrophilic group The group of base reaction and the monomer of free redical polymerization carbon-carbon double bond carry out sudden reaction and prepare.
Polyalcohol can be commonly used in the art in preparing those of polyurethane.However, it is preferred to the molecular weight of the polyalcohol For 400-4000g/mol, preferably 600-3000g/mol.It is 20-200mgKOH/g, preferably 40- that preferred polyol, which is selected from hydroxyl value, 120mgKOH/g, the pure and mild polyether polyol of the polyester polyols of more preferable 50-100mgKOH/g.
It is preferable to use the polyester polyol obtained and reacting dihydric alcohol with dicarboxylic acids.Except free dicarboxylic acids Outside, corresponding dicarboxylic acid anhydride also can be used to prepare polyester polyol.Dicarboxylic acids can be aliphatic series, cyclic aliphatic, araliphatic, virtue Race or heterocycle.Example is suberic acid, azelaic acid, phthalic acid and M-phthalic acid, phthalic anhydride, tetrahydro neighbour benzene two Formic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, Nadic anhydride, glutaric anhydride and Maleic anhydride, maleic acid, fumaric acid and dimer (fatty acid) yl.Preferred formula HOOC- (CH2)yThe dicarboxylic acids of-COOH, wherein y is 1-20 Number, the preferred even number of 2-20, example is succinic acid, adipic acid, decanedioic acid and dodecanedicarboxylic acid.Suitable dihydric alcohols example is Ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, neopentyl glycol, bis- (hydroxyls Ylmethyl) bis- (hydroxymethyl) hexamethylenes of hexamethylene such as Isosorbide-5-Nitrae-, 2- methyl-1,3-propanediol, methyl pentanediol and two are sweet The polyethylene glycol of alcohol, triethylene glycol, tetraethylene glycol, molecular weight less than 1000g/mol, dipropylene glycol, molecular weight are less than 1000g/mol's Polypropylene glycol, dibutylene glycol and molecular weight are less than the polytetramethylene glycol of 1000g/mol.Preferred formula HO- (CH2)xThe alcohol of-OH, wherein x For the number of 1-20, the preferably even number of 2-20.The example of this kind of alcohol is ethylene glycol, 1,4- butanediol, 1,6-HD, 1,8- pungent two Pure and mild 1,12- dodecanediol.
It also suitable is polycarbonate glycol, such as can be by making phosgene and the excessive synthesis as polyester polyol The low molecular weight diol reaction that component refers to obtains.
Polyester-diol based on lactone is also that suitably, these polyester-diols are the homopolymer or copolymer of lactone, preferably The terminal hydroxy group adduct of lactone and suitable bifunctional starting molecule.Suitable lactone is preferably that those are originated from formula HO- (CH2)z- The lactone of the compound of COOH, wherein z is that a hydrogen in 1-20 and methylene units can also be by C1-C4Alkyl replaces.It is suitable to rise The example of beginning component is the low molecular weight diol referred to as the synthesis component of polyester polyol.Particularly preferred polycaprolactone two Alcohol.
Other Suitable polyols are polyetherdiol.They can especially be obtained by the following method: for example in BF3In the presence of Make itself addition polymerization of ethylene oxide, propylene oxide, epoxy butane, tetrahydrofuran, styrene oxide or epichlorohydrin；Or make these Compound is if applicable as a mixture or successively in the starting ingredient containing reactive hydrogen as addition on alcohol or amine is anti- It answers, wherein the starting ingredient is, for example, water, ethylene glycol, 1,2-PD, 1,3-PD, 1,2- bis- (4- hydroxy diphenyls) Propane or aniline.
, according to the invention it is preferred to be used to prepare the polyhydric alcohols for example Polyoxyethylene glycol, polypropylene oxide of polyurethane Glycol, poly- (ethylene oxide-propylene oxide) glycol, polytetrahydrofuran diol, polycarbonate glycol, poly adipate succinic acid ester two Alcohol, polyneopentyl glycol adipate glycol, polyhexamethylene adipate glycol, polycaprolactone glycol and its mixture, it is preferably poly- Erythritan, particularly preferred molecular weight are the polytetrahydrofuran two of 500-4 000g/mol, especially 800-3500g/mol Alcohol.
Polyisocyanates can be commonly used in the art in preparing those of polyurethane, in particular diisocyanate X (NCO)2, Wherein X is the aliphatic hydrocarbyl with 4-12 carbon, cyclic aliphatic or aromatic hydrocarbyl with 6-15 carbon or with 7-15 carbon Araliphatic hydrocarbon radical.
The example of this kind of diisocyanate is tetramethylene diisocyanate, hexamethylene diisocyanate, 12 methylenes Group diisocyanate, 1,4- diisocyanate root trimethylcyclohexane, isophorone diisocyanate, bis- (the 4- isocyano cyclizations of 2,2- Hexyl)-propane, trimethylhexane diisocyanate, 1,4- diisocyanate root conjunction benzene, 2,4 toluene diisocyanate, 2,6- first Phenylene diisocyanate, '-diphenylmethane diisocyanate, benzene dimethylene diisocyanate, tetramethyl are for phenylenedimethylidyne diisocyanate Ester (TMXDI), polyphenyl polymethylene polyisocyanates and its mixture.These isocyanates can be commercially available.
The molar ratio of polyalcohol and polyisocyanates is 0.1:1-0.6:1, preferably 0.2:1-0.4:1.
According to the present invention, polyurethane includes hydrophilic group.Hydrophilic group can come from the chain extender comprising hydrophilic group.It is described to include The chain extender of hydrophilic group is for example selected from 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid, 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid Sodium, 1,4- butanediol -2- sodium sulfonate, second diamino ethanesulfonic acid sodium and second dihydroxy ethanesulfonic acid sodium.
The dosage of the chain extender comprising hydrophilic group is, for example, 1-10 weight %, preferably 2-8 weight %, more preferable 4-7 Weight %, on the basis of the sum of each component weight for being used to prepare polyurethane.
In addition to it is above-mentioned comprising the chain extender of hydrophilic group other than, be additionally added during preparing polyurethane and be usually used in polyurethane The small molecule chain extender of preparation.The molecular weight of the small molecule chain extender is usually less than 300g/mol, preferably 60-200g/mol. Chain extender preferably have 2 to the reactive hydroxyl of isocyanates or amino.Possible chain extender is, for example, to have 2-14, It is preferred that aliphatic, the alicyclic and/or araliphatic glycol of 2-10 carbon atom, such as ethylene glycol, 1,3-PD, 1, the 10- last of the ten Heavenly stems two Alcohol, 1,2-, 1,3-, Isosorbide-5-Nitrae-dihydroxy butylcyclohexane, diethylene glycol (DEG), dipropylene glycol and 1,4-butanediol, 1,6- hexylene glycol and two (2- hydroxyls Base ethyl) quinhydrones, triol, such as 1,2,4- and 1,3,5- trihydroxy hexamethylenes, glycerol and trimethylolpropane, and based on oxidation Ethylene and/or 1,2- propylene oxide and as the above-mentioned glycol of initiator and/or the low molecular weight hydroxyl polyoxyalkylene of triol. As chain extender, can also use general structure is H2N-(CH2)m-NH2(m=2-10) binary amine compound, 2- methyl- 1,5- pentanediamine etc..Particularly preferably use ethylene glycol, 1,4- butanediol, 1,6- butanediol and 2- methyl-1,5- pentanediamine or its Mixture is as small molecule chain extender.
The dosage of the small molecule chain extender is, for example, 1-10 weight %, preferably 2-8 weight %, more preferable 3-6 weight %, On the basis of the sum of each component weight for being used to prepare polyurethane.
According to the present invention, the carbon-carbon double bond of a small amount of free redical polymerization is introduced in polyurethane molecular, then can then be led to It crosses free radical polymerization the monomers such as styrene, butadiene are copolymerized in polyurethane molecular chain.Free redical on polyurethane molecular Polymerization carbon-carbon double bond can be by being added in the preparation process of polyurethane with the group that can be reacted with isocyanate group and can oneself It is introduced by the monomer of the carbon-carbon double bond of base polymerization.
The monomer of the carbon-carbon double bond with the group and free redical polymerization that can react with isocyanate group for example selects From with 1-10 carbon atom glycol with the α of 3-10 carbon atom, the β-olefinic mono- and/or dicarboxylic acids of unsaturation and its The ester of acid anhydrides.The example of the unsaturated mono- and/or dicarboxylic acids of utilizable α, β-olefinic and its acid anhydrides includes acrylic acid, methyl Acrylic acid, fumaric acid, maleic acid, maleic anhydride, crotonic acid, itaconic acid etc..The example of suitable glycol be with 1-10, preferably 2-8, the glycol of more preferable 2-6 carbon atom, such as ethylene glycol, 1,2-PD, 1,3-PD, 1,1- Dimethyl -1,2- ethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2- ethyl -1,3- propylene glycol, 2- methyl-1,3- the third two Alcohol, neopentyl glycol, neopentyl glycol hydroxy new pentane acid ester, 1,2- butanediol, 1,3 butylene glycol or 1,4- butanediol, 1,6- oneself two Alcohol, 1,10- decanediol, cyclohexane diol etc..It is preferred that (methyl) acrylic acid C1-C8Hydroxyalkyl acrylate, more preferable (methyl) acrylic acid C2-C6Hydroxyalkyl acrylate.
The monomer of the carbon-carbon double bond with the group and free redical polymerization that can react with isocyanate group can be with It is the acrylamide with hydroxyl, such as the bis- (C of N, N-2-C6Hydroxyalkyl) acrylamide.
In a preferred embodiment of the invention, described with the group that can be reacted with isocyanate group and can be free The monomer of the carbon-carbon double bond of base polymerization is selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, metering system Sour hydroxypropyl acrylate and N, bis- (2- ethoxy) acrylamides of N-.
The dosage example of the monomer with the group and free redical polymerization carbon-carbon double bond that can be reacted with isocyanate group For example 0.1-5 weight %, preferably 0.2-2 weight %, more preferable 0.3-1 weight %, to be used to prepare each component weight of polyurethane On the basis of the sum of amount.
Polyurethane and Carboxy copolymer are via covalent bond in polyurethane-modified Carboxy copolymer of the invention Connection.
In one embodiment of the invention, the Carboxy copolymer matrix is in the Carboxy copolymer weight packet The % of weight containing 1-15, preferably 1.5-12 weight %, the monoethylenically unsaturated carboxylic acid monomeric unit of more preferable 2-8 weight %.
The monoethylenically unsaturated carboxylic acid is selected from monoene and belongs to unsaturation C3-C10Monocarboxylic acid, monoene belong to unsaturation C4-C10Dicarboxyl Acid and its acid anhydrides, preferably monoene belong to unsaturation C3-C6Monocarboxylic acid, monoene belong to unsaturation C4-C8Dicarboxylic acids and its acid anhydrides.For example, institute Stating monoethylenically unsaturated monocarboxylic can be selected from acrylic acid and methacrylic acid.The monoene belongs to unsaturation C4-C10Dicarboxylic acids is optional From itaconic acid, fumaric acid, mesaconic acid, maleic acid, citraconic acid and dimethyl maleic acid.
Other than styrene, butadiene and monoethylenically unsaturated carboxylic acid monomeric unit, the Carboxy copolymer can Optionally comprising other one or more single ethylenically unsaturated monomer units.The monomer is, for example, to have satisfying for 1-6 carbon atom Such as with vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and the vinyl ethers of carboxylic acid C1-C6Alkyl vinyl ether such as methyl vinyl ether or ethyl vinyl ether.Other suitable comonomer is olefinic unsaturation C3-C6Ester, amide and the nitrile of carboxylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid second Ester, butyl acrylate and butyl methacrylate, acrylamide and Methacrylamide and acrylonitrile and methacrylonitrile.
According to the present invention, the Carboxy copolymer can contain 0-15 weight based on the Carboxy copolymer weight Measure %, preferably 0-10 weight %, other single ethylenically unsaturated monomer units of more preferable 3-8 weight %.
In one embodiment of the invention, the Carboxy copolymer can also include cross-linker monomer units. Suitable crosslinking agent includes two (methyl) acrylate of the saturation dihydric alcohol containing 2-6 carbon atom, has more than 2 hydroxyls Alcohol (methyl) acrylate, ethylene oxide and/two (methyl) acrylate of propylene oxide oligomer, (methyl) acrylic acid Ester vinyl acetate, butanediol divinyl ether, trimethylolpropane tris vinyl ethers, (methyl) allyl acrylate, pentaerythrite Triallyl ether, methylene two (methyl) acrylamide, divinylbenzene etc..
Two (methyl) acrylate of saturation dihydric alcohol containing 2-6 carbon atom can be selected from glycol diacrylate, Ethylene glycol dimethacrylate, 1,2-PD diacrylate, 1,2-PD dimethylacrylate, butanediol two (methyl) acrylate, such as butane-Isosorbide-5-Nitrae-omega-diol diacrylate, butane-Isosorbide-5-Nitrae-diol dimethacrylate, hexylene glycol two Acrylate, hexanediol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, 3- first Base Diacrylate and 3- methyl pentanediol dimethylacrylate.
The example of (methyl) acrylate with the alcohol more than 2 hydroxyls include trimethylolpropane trimethacrylate and Trimethylol-propane trimethacrylate.
The example of two (methyl) acrylate of ethylene oxide and/or propylene oxide oligomer is diethylene glycol (DEG) diacrylate Ester, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate Ester and tetraethylene glycol dimethacrylate.
According to the present invention, the Carboxy copolymer matrix contains 0-3 weight % in the Carboxy copolymer weight, excellent Select 0-1 weight %, the cross-linker monomer units of more preferable 0.1-0.5 weight %.
In one embodiment of the invention, butadiene and styrenic monomer units weight in the Carboxy copolymer The sum of amount is 70-98 weight %, preferably 80-97 weight %, more preferable 85-96 weight based on the Carboxy copolymer weight Measure %.
In the Carboxy copolymer, the weight ratio of butadiene unit and styrene units can be 0.5:1-5:1, It is preferred that 0.7:1-3:1, more preferable 0.9:1-2:1.
The latex according to the present invention comprising polyurethane-modified Carboxy copolymer is prepared the present invention also provides a kind of Method comprising
A) there is the polyurethane of free redical polymerization carbon-carbon double bond and hydrophilic group by sudden reaction preparation, and
B) in the presence of the polyurethane with free redical polymerization carbon-carbon double bond and hydrophilic group obtained by step a), pass through Emulsion polymerization prepares Carboxy copolymer, obtains the latex comprising polyurethane-modified Carboxy copolymer.
According to the present invention, step a) can be carried out as follows, wherein making polyalcohol and polyisocyanates in the presence of a catalyst Carry out sudden reaction, then further with containing hydrophilic group chain extender, another small molecule chain extender and have can be with isocyanic acid The group of ester group reaction and the monomer of free redical polymerization carbon-carbon double bond carry out sudden reaction.
In order to accelerate the reaction of isocyanates, conventional catalyst can be used.Those of appropriate in principle is polyurethane Common all catalyst in chemistry.
These are, for example, organic amine, especially tertiary aliphatic, alicyclic or aromatic amine and/or lewis acidic are had Machine metallic compound.The example of lewis acidic organo-metallic compound appropriate includes tin compound, such as the tin of organic carboxyl acid (II) dioxane of salt such as tin acetate (II), tin octoate (II), thylhexoic acid tin (II) and tin laurate (II) and organic carboxyl acid Ji Xi (IV) salt, such as dimethyltin diacetate, dibutyltin diacetate, two butyric acid dibutyl tins, bis- (2 ethyl hexanoic acid) two fourths Ji Xi, dibutyl tin dilaurate, dibutyitin maleate, the pungent tin of tin dilaurate two and the pungent tin of oxalic acid two.Gold can also be used Belong to the acetylacetonate of complex compound such as iron, titanium, aluminium, zirconium, magnesium, nickel and cobalt.
Preferred lewis acidic organo-metallic compound is tin octoate (II), dimethyltin diacetate, two butyric acid, two fourth Ji Xi, bis- (2 ethyl hexanoic acid) dibutyl tins, dibutyl tin dilaurate, tin dilaurate dioctyl tin, zirconium acetylacetonate and The diketonate zirconium of 2,2,6,6- tetramethyl -3,5- heptane.
There are also bismuths and Co catalysts and cesium salt, can be used as catalyst.Cesium salt appropriate include wherein using following yin from Those of son compound: F-、Cl-、ClO-、ClO3 -、ClO4 -、Br-、I-、IO3 -、CN-、OCN-、NO2 -、NO3 -、HCO3 -、CO3 2-、 S2-、SH-、HSO3 -、SO3 2-、HSO4 -、SO4 2-、S2O2 2-、S2O4 2-、S2O5 2-、S2O6 2-、S2O7 2-、S2O8 2-、H2PO2 -、H2PO4 -、 HPO4 2-、PO4 3-、P2O7 4-、(OCnH2n+1)-、(CnH2n-1O2)-、(CnH2n-3O2)-(Cn+1H2n-2O4)2-, the number of n expression 1 to 20.
It is preferred that carboxylic acid caesium, wherein anion meeting formula (CnH2n-1O2)-(Cn+1H2n-2O4)2-, n be 1 to 20 number.Especially Preferably comprising general formula is (CnH2n-1O2)-Monocarboxylic acid anion cesium salt, wherein n indicate 1 to 20 number.It especially answers herein Mention formates, acetate, propionate, caproate and 2 ethyl hexanoic acid salt.
According to the present invention, catalyst can be based on the polyol component and polyisocyanate component weight for being used to prepare polyurethane The sum of amount is with 0.05-1 weight %, preferably 0.08-0.5 weight % use.
Sudden reaction in step a) can carry out at a temperature of preferably 60-85 DEG C at 40-90 DEG C.Reaction time can be with It is 1.5-10 hours, it is preferably 2-8 hours, 3-6 hours more preferable.
According to the present invention, step b), which is included in, has free redical polymerization carbon-carbon double bond and hydrophilic group by what step a) was obtained Polyurethane in the presence of, Carboxy copolymer is prepared by emulsion polymerization, obtain comprising polyurethane-modified Carboxy be copolymerized The latex of object.
Since the polyurethane obtained by step a) contains free redical polymerization carbon-carbon double bond, therefore can be passed through by graft reaction Radical polymerization mechanism will be in styrene, butadiene, unsaturated acids and other vinyl monomer copolymerizations to polyurethane molecular chain.
In one embodiment of the invention, the emulsion polymerization in step b) carries out in the presence of emulsifier.Suitably Emulsifier includes anion, cation and nonionic surfactant.It is preferable to use anionic surfactants and nonionic table Face activating agent and Anionic-nonionic complexed surfactant.
Preferred anionic surfactant includes C8-C18Saturation or unsaturated fatty acid salt, such as oleic acid, linoleic acid, Asia Numb acid, palmitinic acid, stearic acid, myristic acid, lauric acid, rosin acid sodium salt or sylvite；Alkylsurfuric acid (alkyl: C8-C12) Alkali metal salt and ammonium salt, such as lauryl sodium sulfate；Alkyl aryl sulphonic acid (alkyl: C9-C18) alkali metal salt and ammonium salt, such as ten Dialkyl benzene sulfonic acids sodium；Alkyl biphenyl ether sodium disulfonate etc.；Common non-ionic surfactants for example ethoxylated fat Alcohol (EO unit: 3-50, alkyl: C8-C36), ethoxylation is mono-, two- and trialkyl phenol (EO unit: 3-50, alkyl: C4-C9), Preferred nonionic emulsifier includes OP series, Tween series and Span series, for example, OP-10, OP-20, Tween-20, Tween-60, Span-60, Span-80 etc..
According to an embodiment, the emulsion polymerization in step b) is being 0-1 weight % based on system total weight, preferably It is carried out in the presence of the emulsifier of 0.1-0.5 weight %.
According to the present invention it is possible to use less, or even does not use emulsifier and prepare Carboxy copolymer.Of the invention In another preferred embodiment, the emulsion polymerization in step b) can be carried out in the case where being added without emulsifier.
In a preferred embodiment of the invention, step is being carried out after the method for the present invention is included in step a) and terminates B) before, a part is introduced into reaction system, preferably 3-50 weight %, more preferable 10-30 weight %'s is used to prepare carboxyl The monomer of butylbenzene copolymer, optional neutralizer and water obtain polyaminoester emulsion.
Then, initiator can be added into the polyaminoester emulsion and carry out emulsion polymerization, then add remaining for making Monomer, optional emulsifier, the initiator of standby Carboxy copolymer are polymerize, and are obtained total comprising polyurethane-modified Carboxy The latex of polymers.
Hydrophilic group on polyurethane is acidic-group, and under carboxyl or sulfonic situation, neutralizer progress can be added It neutralizes.Neutralizer can be selected from organic amine, alkali metal hydroxide and ammonium hydroxide, preferably triethylamine, tripropyl amine (TPA), sodium hydroxide and ammonia Water.
Radical initiator is one or more of water-soluble and oleosoluble radical initiators, preferably persulfate and Redox initiator systems.Wherein water soluble starter specifically includes that ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, azo two NSC 18620 hydrochloride, two isobutyl imidazoline hydrochloride of azo；Oil-soluble initiator specifically includes that azodiisobutyronitrile, azo two Different heptonitrile, azo-bis-iso-dimethyl, azo isobutyl cyano formamide, dibenzoyl peroxide, tert-butyl hydroperoxide, mistake Hydrogen oxide isopropylbenzene.
Redox initiator systems are made of reducing agent and oxidant.
Oxidation component is for example including the above-mentioned initiator having been mentioned for emulsion polymerization.
Alkali metal salt of the reduction components for example including sulfurous acid such as sodium sulfite, sodium hydrogensulfite, the alkali gold of pyrosulfurous acid Belong to salt such as sodium pyrosulfite, bisulfite adduct such as rongalite or the reducing agent such as hydroxyl first of aliphatic aldehydes and ketone Alkane sulfinic acid and its salt or ascorbic acid, ferrous sulfate, glucose.
The example of conventional Redox initiator systems includes ascorbic acid/ferrous sulfate/sodium peroxydisulfate, tert-butyl mistake Hydrogen oxide/sodium pyrosulfite, tert-butyl hydroperoxide/hydroxy methane sulfinic acid sodium, cumyl hydroperoxide/ferrous sulfate/Portugal Grape sugar.
It is 0.1-5 weight that the amount of initiator, which is typically based on and is used to prepare the total weight monomer to be polymerized of Carboxy copolymer, Measure %, preferably 0.5-2 weight %.
For polymerizeing every 100 parts also usable such as 0-0.8 parts by weight regulators monomer to be polymerized.
The regulator reduces the molal weight of polymer.Suitable example includes such as uncle of the compound containing thiol base Butanethiol, mercaptopropyi trimethoxy silane and tert-dodecylmercaotan.
Properly, other auxiliary agents can also be added, in electrolyte, chelating agent, pH adjusting agent or buffer, defoaming agent It is one or more.
In emulsion polymerization, electrolyte, which is added, can be improved stability, reduces emulsifier and control partial size.These electrolysis Matter is, for example, sodium chloride or potassium chloride.The dosage of electrolyte is usually less than 0.1 weight %, preferably 0.02-0.5 weight %, more excellent 0.08-0.4 weight % is selected, on the basis of the total weight monomer to be polymerized for being used to prepare Carboxy copolymer.
Emulsion polymerization carries out at preferably 50-90 DEG C usually at 30-130 DEG C.
Polymerisation medium can only be made of water or be made of the mixture of water and water miscibility liquid such as methanol.It is preferred that only making Use water.
The preparation process of the latex comprising polyurethane-modified Carboxy copolymer includes disposable feeding method, partly connects Continuous method, pre-emulsifying method and continuity method.It is preferred that using semi-continuous process and pre-emulsifying method.
The detailed process of the semi-continuous process is:
After preparing polyurethane, part is added, preferably 3-50 weight %, more preferable 10-30 weight % grafted monomers are (i.e. It is used to prepare the monomer of Carboxy copolymer) it reduces viscosity and neutralizer is added is neutralized, then this mixed liquor is heated To reaction temperature.A part, the preferably initiator of 20-50 weight % is added, wherein can be molten in advance for water soluble starter Yu Shui can be previously dissolved in grafted monomers for oil-soluble initiator.Finally remaining grafted monomers and remaining initiator are pressed It is added drop-wise in polymerization system respectively according to certain rate, such as through 2-5 hours, the reaction was continued after completion of dropwise addition 3-5 hours.
The detailed process of the pre-emulsifying method is:
After preparing polyurethane, part is added, preferably 3-50 weight %, more preferable 10-30 weight % grafted monomers are (i.e. It is used to prepare the monomer of Carboxy copolymer) it reduces viscosity and neutralizer is added is neutralized, then this mixed liquor is heated To reaction temperature.A part, the preferably initiator of 20-50 weight % is added, wherein can be molten in advance for water soluble starter Yu Shui can be previously dissolved in grafted monomers for oil-soluble initiator.Then by optional emulsifier solution, remaining grafted monomers with And remaining initiator presses given pace by online-emulsification (such as via a pipeline emulsifier) afterwards, such as is added through 2-5 hours The reaction was continued into polymerization reaction system, after charging 2-5 hours.
Gained includes that the solid content of the latex of polyurethane-modified Carboxy copolymer is usually 20-60 weight %, preferably 30-50 weight %.
In the latex that gained includes polyurethane-modified Carboxy copolymer, the average grain diameter of polymer beads is preferably small In 300nm, especially less than 250nm, particularly preferred average grain diameter is between 100-250nm.Partial size for example can be used international logical Precision instrument Zetasize 3000HS (Malvern company, Britain) measurement.
In the latex comprising polyurethane-modified Carboxy copolymer of the invention, polyurethane is on butylbenzene copolymer Grafting rate is 90-99.5 weight %, such as 94-99 weight % or 95-98 weight %.The grafting rate can for example pass through acetone Extraction process measurement.Since acetone is the good solvent of polyurethane, extract get off be not with butylbenzene copolymer grafting polyurethane:
Polyurethane is in the grafting rate on Carboxy copolymer=(be grafted to the weight of the polyurethane on Carboxy copolymer Measure/be used to prepare the total weight of the monomer of polyurethane) × 100%.
Remaining polymer weight-is used to prepare after the weight=extracting for the polyurethane being grafted on Carboxy copolymer The total weight of the monomer of Carboxy copolymer
Latex of the present invention can be used as adhesive for carpet manufacture, building, papermaking, leather, textile printing and dyeing and cement, especially It is for carpet manufacture.
Specific embodiment
The solution of the present invention is explained below in conjunction with example.It will be appreciated by those skilled in the art that following Embodiment is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Particular technique or item are not specified in embodiment Part, it is carried out according to technology or conditions described in the document of this field or product description.Part mentioned in this article refers to parts by weight.
Embodiment 1-includes the latex of polyurethane-modified Carboxy copolymer
250 parts of polyetherdiol N210 (being purchased from Beijing Linshi Fine New Material Co., Ltd.), 222 parts of isophorones two are different Cyanate and 1 part of dibutyl tin dilaurate are added in autoclave, react 2 hours after being heated with stirring to 80 DEG C；Then plus Enter 29.6 parts of dimethylolpropionic acids, 31.5 parts of 1,4- butanediols react 4 hours at 80 DEG C；3.48 parts are added after being cooled to 70 DEG C Hydroxy-ethyl acrylate, the reaction was continued 2 hours；The mixed liquor that 150 parts of styrene and 350 parts of butadiene are added after being cooled to 30 DEG C stirs Viscosity reduction is mixed, 15.2 parts of triethylamines are then added and neutralize, 11880 parts of deionized waters are added after twenty minutes, stir 40 minutes, is obtained same The polyaminoester emulsion of Shi Hanyou free redical polymerization carbon-carbon double bond and carboxyl.
The stirring of above-mentioned system is warming up to 80 DEG C, after twenty minutes, (initiator is water-soluble by 2000 parts of initiator solutions for stirring Liquid is prepared and 101 parts of ammonium persulfates are previously dissolved in 2980 parts of deionized waters) it is added to initiation reaction in system, it reacts Emulsifier aqueous solution (56 parts of lauryl sodium sulfate, 18 parts of potassium chloride and 8900 parts of deionized waters) are added after 1 hour, then will Remaining grafted monomers (4400 parts of styrene, 4776 parts of butadiene, 204 parts of acrylic acid, 300 parts of acrylonitrile, 25 parts of divinyl Benzene) and 30 parts of tert-dodecylmercaotans mixture and remaining initiator solution be added drop-wise in system respectively, time for adding 2 Hour, the reaction was continued after completion of dropwise addition 5 hours, then obtains within vacuum outgas 3 hours at 80 DEG C comprising polyurethane-modified carboxyl The latex of butylbenzene copolymer, it is 96.4% that acetone extraction method, which measures grafting rate of the polyurethane on butylbenzene copolymer,.Products therefrom Solid content, viscosity and particle size data be shown in Table 1, wherein partial size use international precision instrument Zetasize 3000HS (English Malvern company, state) measurement.
Embodiment 2-includes the latex of polyurethane-modified Carboxy copolymer
700 parts of polyetherdiol N220 (being purchased from Beijing Linshi Fine New Material Co., Ltd.), 250 parts of diphenyl-methanes two are different Cyanate and 1 part of dibutyl tin dilaurate are added in autoclave, react 1.5 hours after being heated with stirring to 80 DEG C；Then 22.2 parts of dimethylolpropionic acids are added, 31.6 parts of 1,4- butanediols react 4 hours at 75 DEG C；5.2 are added after being cooled to 70 DEG C Part hydroxyethyl methacrylate, the reaction was continued 2 hours；Mixing for 360 parts of styrene and 540 parts of butadiene is added after being cooled to 30 DEG C It closes liquid and stirs viscosity reduction, 14.3 parts of triethylamines are then added and neutralize, 7560 parts of deionized waters are added after twenty minutes, stir 45 minutes, Obtain the polyaminoester emulsion containing free redical polymerization carbon-carbon double bond and carboxyl simultaneously.
The stirring of above-mentioned system is warming up to 75 DEG C, emulsifier aqueous solution (82 parts of neopelexes, 18 are then added Part potassium chloride and 5670 parts of deionized waters), after stirring 30 minutes, by 1000 parts of initiator solutions, (initiator solution passes through 106 parts of potassium peroxydisulfates are previously dissolved in 1890 parts of deionized waters and are prepared) it is added to initiation reaction in system, while will be remaining Grafted monomers (3820 parts of styrene, 3530 parts of butadiene, 360 parts of methacrylic acids, 108 parts of ethylene glycol dimethacrylates) It is added drop-wise in system respectively with the mixture of 7 parts of tert-dodecylmercaotans and remaining initiator solution, time for adding is 2 small When, the reaction was continued after completion of dropwise addition 6 hours, and then vacuum outgas 3 hours at 75 DEG C, obtain comprising polyurethane-modified carboxyl fourth The latex of benzene copolymer, it is 95.3% that acetone extraction method, which measures grafting rate of the polyurethane on butylbenzene copolymer,.Products therefrom Solid content, viscosity and particle size data are shown in Table 1, and wherein partial size uses international precision instrument Zetasize 3000HS (Britain Malvern company) measurement.
Embodiment 3-includes the latex of polyurethane-modified Carboxy copolymer
By 600 parts of polycaprolactone glycols (molecular weight 2000, hydroxyl value about 50mg KOH/g), 168 parts of two isocyanides of hexa-methylene Acid esters and 0.8 part of stannous octoate are added in autoclave, react 1.5 hours after being heated with stirring to 80 DEG C；Then 40.2 are added Part dihydromethyl propionic acid, 29.5 parts of 1,6-HDs react 3 hours at 85 DEG C；7 parts of metering systems are added after being cooled to 75 DEG C Sour hydroxypropyl acrylate, the reaction was continued 2.5 hours；The mixed liquor that 250 parts of styrene and 460 parts of butadiene are added after being cooled to 35 DEG C stirs Then viscosity reduction is added 26.2 parts of triethylamines and neutralizes, 2813 parts of deionized waters are added after twenty minutes, stirs 40 minutes, obtains simultaneously Polyaminoester emulsion containing free redical polymerization carbon-carbon double bond and carboxyl.
After the stirring of above-mentioned system is warming up to 85 DEG C, stirring 50 minutes, by 400 parts of initiator solutions, (initiator is water-soluble Liquid is prepared and 55 parts of sodium peroxydisulfates are previously dissolved in 700 parts of deionized waters) it is added to initiation reaction in system, reaction 2 Emulsifier aqueous solution (35 parts of alkyl biphenyl ether sodium disulfonates, 7 parts of sodium chloride and 2100 parts of deionized waters) are added after hour, simultaneously By remaining grafted monomers (1950 parts of styrene, 1550 parts of butadiene, 286 parts of methacrylic acids, 12 parts of diacrylate -1,6- oneself Diol ester) and 9 parts of tert-dodecylmercaotans mixture and remaining initiator solution be added drop-wise in system respectively, time for adding It is 2.5 hours, the reaction was continued after completion of dropwise addition 5 hours, and then vacuum outgas 3 hours at 80 DEG C, obtain changing comprising polyurethane Property Carboxy copolymer latex, acetone extraction method measure grafting rate of the polyurethane on butylbenzene copolymer be 97.6%.Institute Solid content, viscosity and the particle size data for obtaining product are shown in Table 1, and wherein partial size uses international precision instrument Zetasize 3000HS (Malvern company, Britain) measurement.
Embodiment 4-includes the latex of polyurethane-modified Carboxy copolymer
400 parts of polyetherdiol N210 (being purchased from Beijing Linshi Fine New Material Co., Ltd.), 222 parts of isophorones two are different Cyanate and 0.8 part of stannous octoate are added in autoclave, react 2 hours after being heated with stirring to 80 DEG C；Then 17.4 are added Part dimethylolpropionic acid, 28 parts of ethylene glycol react 3 hours at 80 DEG C；4.9 parts of hydroxyethyl methacrylates are added after being cooled to 70 DEG C Ethyl ester, the reaction was continued 2 hours；The mixed liquor that 160 parts of styrene and 380 parts of butadiene are added after being cooled to 30 DEG C stirs viscosity reduction, Then 5.5 parts of triethylamines are added to neutralize, 3082 parts of deionized waters are added after forty minutes, stir 60 minutes, obtain simultaneously containing can The polyaminoester emulsion of free radical polymerization carbon-carbon double bond and carboxyl.
After the stirring of above-mentioned system is warming up to 75 DEG C, stirring 15 minutes, by 500 parts of initiator solutions, (initiator is water-soluble Liquid is prepared and 9 parts of cumyl hydroperoxides, 5 parts of ferrous sulfate, 5 parts of glucose are previously dissolved in 770 parts of deionized waters) It is added to initiation reaction in system, by emulsifier aqueous solution (18 parts of sodium laurates, 8 parts of Span-60,8 parts of chlorine after reaction 1 hour Change potassium and 2311 parts of deionized waters), remaining grafted monomers (920 parts of styrene, 880 parts of butadiene, 212 parts of acrylic acid, 106 parts Acrylonitrile, 6 parts of divinylbenzenes) and 2.6 parts of tert-dodecylmercaotans mixture and remaining initiator solution pass through a pipe It is added dropwise after road emulsifier online-emulsification and enters polymerization reaction system, time for adding is 2 hours, and the reaction was continued after completion of dropwise addition 4.5 Hour, then vacuum outgas 3 hours at 75 DEG C, obtain the latex comprising polyurethane-modified Carboxy copolymer, and acetone is taken out It is 96.6% that formulation, which measures grafting rate of the polyurethane on butylbenzene copolymer,.Solid content, viscosity and the particle size data of products therefrom It is shown in Table 1, wherein partial size is measured using international precision instrument Zetasize 3000HS (Malvern company, Britain).
Embodiment 5-includes the latex of polyurethane-modified Carboxy copolymer
By 500 parts of polytetrahydrofuran diols (molecular weight 2000, hydroxyl value about 50mg KOH/g), 174 parts of 2,4- toluene two Isocyanates and 1 part of dibutyl tin dilaurate are added in autoclave, react 3 hours after being heated with stirring to 80 DEG C；Then 37 parts of dimethylolpropionic acids, 46.4 parts of 2- methyl-1s are added, 5- pentanediamine reacts 4 hours at 73 DEG C；Add after being cooled to 70 DEG C Enter 2.6 parts of hydroxyethyl methacrylates, the reaction was continued 1 hour；120 parts of styrene and 420 parts of fourths two are added after being cooled to 30 DEG C The mixed liquor of alkene stirs viscosity reduction, and 25.2 parts of triethylamines are then added and neutralize, and 1857 parts of deionized waters, stirring 50 are added after 26 minutes Minute, obtain the polyaminoester emulsion containing free redical polymerization carbon-carbon double bond and carboxyl simultaneously.
After the stirring of above-mentioned system is warming up to 80 DEG C, stirring 30 minutes, by 300 parts of initiator solutions, (initiator is water-soluble Liquid is prepared and 17 parts of cumyl hydroperoxides, 9 parts of ferrous sulfate, 9 parts of glucose are first dissolved in 464 parts of deionized waters) It is added to initiation reaction in system, by emulsifier aqueous solution (10 parts of enuatrols, 6 parts of Span-20,3 parts of chlorinations after reaction 1 hour Sodium and 1393 parts of deionized waters), remaining grafted monomers (670 parts of styrene, 850 parts of butadiene, 114 parts of acrylic acid, 60 parts of methyl Butyl acrylate) and 3 parts of tert-dodecylmercaotans mixture and remaining initiator solution it is online by a pipeline emulsifier Reaction system is added drop-wise to after emulsification, time for adding is 2 hours, and the reaction was continued after completion of dropwise addition 4.5 hours, then true at 80 DEG C Sky degassing 3 hours, obtains the latex comprising polyurethane-modified Carboxy copolymer, acetone extraction method measures polyurethane in butylbenzene Grafting rate on copolymer is 98.1%.Solid content, viscosity and the particle size data of products therefrom are shown in Table 1, and wherein partial size uses state The general precision instrument Zetasize 3000HS in border (Malvern company, Britain) measurement.
Embodiment 6-includes the latex of polyurethane-modified Carboxy copolymer
500 parts of polyetherdiol N220 (being purchased from Beijing Linshi Fine New Material Co., Ltd.), 250 parts of diphenyl-methanes two are different Cyanate and 1 part of dibutyl tin dilaurate are added in autoclave, react 3 hours after being heated with stirring to 80 DEG C；Then plus Enter 45 parts of dihydromethyl propionic acids, 12.6 parts of 1,4- butanediols react 4 hours at 75 DEG C；8 parts of N, N- are added after being cooled to 70 DEG C Bis- (2- ethoxy) acrylamides, the reaction was continued 2 hours；550 parts of styrene and 1620 parts of butadiene are added after being cooled to 30 DEG C Mixed liquor stir viscosity reduction, 30.5 parts of triethylamines are then added and neutralize, 9415 parts of deionized waters are added after twenty minutes, stir 40 points Clock obtains the polyaminoester emulsion containing free redical polymerization carbon-carbon double bond and carboxyl simultaneously.
The stirring of above-mentioned system is warming up to 70 DEG C, after twenty minutes, (initiator is water-soluble by 1400 parts of initiator solutions for stirring Liquid is prepared and 65 parts of sodium peroxydisulfates are previously dissolved in 2353 parts of deionized waters) it is added to initiation reaction in system, it reacts By sodium chloride solution (14 parts of sodium chloride are dissolved in 7061 parts of deionized waters), remaining grafted monomers (835 parts of benzene second after 1.5 hours Alkene, 1020 parts of butadiene, 217 parts of acrylic acid, 110 parts of butyl acrylates, 10 parts of divinylbenzenes) and 14 parts of tertiary dodecyl sulphur The mixture of alcohol and remaining initiator solution are added dropwise by being added drop-wise to polymerization reaction system after a pipeline emulsifier online-emulsification Time is 2.5 hours, and the reaction was continued after completion of dropwise addition 5.5 hours, and then vacuum outgas 3 hours at 70 DEG C, obtain comprising poly- The latex of urethane modified carboxyl butylbenzene copolymer, acetone extraction method measure grafting rate of the polyurethane on butylbenzene copolymer and are 95.2%.Solid content, viscosity and the particle size data of products therefrom are shown in Table 1, and wherein partial size uses international precision instrument Zetasize3000HS (Malvern company, Britain) measurement.
Comparative example 1- polyaminoester emulsion
400 parts of polyetherdiol N210 (being purchased from Beijing Linshi Fine New Material Co., Ltd.), 222 parts of isophorones two are different Cyanate and 0.8 part of stannous octoate are added in autoclave, react 2 hours after being heated with stirring to 80 DEG C；Then 17.4 are added Part dimethylolpropionic acid, 28 parts of ethylene glycol react 3 hours at 80 DEG C；It is cooled to 30 DEG C and 70 parts of acetone stirring viscosity reductions is added, so 5.5 parts of triethylamines are added afterwards to neutralize, 1732 parts of deionized waters are added after forty minutes, vacuum distillation removes third after sixty minutes for stirring Ketone obtains polyaminoester emulsion.Solid content, viscosity and the particle size data of products therefrom are shown in Table 1, and wherein partial size uses international Precision instrument Zetasize 3000HS (Malvern company, Britain) measurement.
Comparative example 2- carboxyl styrene emulsion
160 parts of styrene, 5 parts of sodium laurates and 1300 parts of water are added in autoclave, lead to nitrogen after ten minutes, it will 380 parts of butadiene are introduced into autoclave, pre-emulsification are stirred at room temperature 1 hour, and then system is warming up to 75 DEG C, are stirred 15 minutes Afterwards, by 500 parts of initiator solutions, (initiator solution is by by 9 parts of cumyl hydroperoxides, 5 parts of ferrous sulfate, 5 parts of Portugals Grape sugar is previously dissolved in 770 parts of deionized waters and prepares) it is added to initiation reaction in system, by emulsifier water after reaction 1 hour Solution (13 parts of sodium laurates, 8 parts of Span-60,8 parts of potassium chloride and 1000 parts of deionized waters), remaining grafted monomers (920 parts of benzene Ethylene, 880 parts of butadiene, 212 parts of acrylic acid, 106 parts of acrylonitrile, 6 parts of divinylbenzenes) and 2.6 parts of tert-dodecylmercaotans Mixture and remaining initiator solution by being added dropwise after a pipeline emulsifier online-emulsification enter polymerization reaction system, be added dropwise Time is 2 hours, and the reaction was continued after completion of dropwise addition 4.5 hours, and then vacuum outgas 3 hours at 75 DEG C, obtain Carboxy Lotion.Solid content, viscosity and the particle size data of products therefrom are shown in Table 1, and wherein partial size uses international precision instrument Zetasize 3000HS (Malvern company, Britain) measurement.
3-polyurethane of comparative example/Carboxy blendlatex
By 1 product of comparative example and 2 product of comparative example according to polyurethane and Carboxy copolymer quality than the ratio for 1:4 Mixing 20 minutes is stirred at room temperature, obtains polyurethane/Carboxy blendlatex.Solid content, viscosity and the grain of products therefrom Diameter data are shown in Table 1, and wherein partial size is surveyed using international precision instrument Zetasize 3000HS (Malvern company, Britain) Amount.
Performance test
It is as a result shown in table 1 according to the properties of latex obtained by the embodiment and comparative example of the standard testing in table 2.
Tufted carpet used is that 400 type tufted carpet of loop pile (is purchased from the new limited public affairs of certain herbaceous plants with big flowers carpet in Jiangmen city Xinhui District in test Department).
Latex of the table 1 comprising polyurethane-modified Carboxy copolymer, polyaminoester emulsion, carboxyl styrene emulsion, polyurethane/ Carboxy blendlatex performance indicator
Table 2: standard used

Claims (23)

1. a kind of latex comprising polyurethane-modified Carboxy copolymer, wherein the polyurethane-modified Carboxy copolymer Middle polyurethane and Carboxy copolymer are via covalent key connection, and the polyurethane includes hydrophilic group,
Wherein the weight ratio of polyurethane and Carboxy copolymer is 40 in the polyurethane-modified Carboxy copolymer: 60-3:97；With
Hydrophilic group on the polyurethane is selected from carboxyl, sulfonic group and its salt,
Wherein the polyurethane is by making polyalcohol and polyisocyanates carry out sudden reaction, then further and containing described hydrophilic The chain extender of base, another small molecule chain extender and with the group and free redical polymerization carbon carbon that can be reacted with isocyanate group The monomer of double bond carries out sudden reaction and prepares, and then has free redical polymerization carbon carbon double what is obtained by the sudden reaction In the presence of the polyurethane of key and hydrophilic group, Carboxy copolymer is prepared by emulsion polymerization, is obtained comprising polyurethane-modified carboxylic The latex of base butylbenzene copolymer,
The dosage of the chain extender comprising hydrophilic group is 1-10 weight %, with the sum of each component weight for being used to prepare polyurethane On the basis of.
2. the latex according to claim 1 comprising polyurethane-modified Carboxy copolymer, wherein described polyurethane-modified The weight ratio of polyurethane and Carboxy copolymer is 30:70-5:95 in Carboxy copolymer.
3. the latex according to claim 1 comprising polyurethane-modified Carboxy copolymer, wherein described polyurethane-modified The weight ratio of polyurethane and Carboxy copolymer is 25:75-8:92 in Carboxy copolymer.
4. the latex according to claim 1 comprising polyurethane-modified Carboxy copolymer, wherein the molecule of the polyalcohol Amount is 400-4000g/mol.
5. the latex according to claim 2 comprising polyurethane-modified Carboxy copolymer, wherein the molecule of the polyalcohol Amount is 400-4000g/mol.
6. the latex according to claim 3 comprising polyurethane-modified Carboxy copolymer, wherein the molecule of the polyalcohol Amount is 400-4000g/mol.
7. the latex according to claim 4 comprising polyurethane-modified Carboxy copolymer, wherein the molecule of the polyalcohol Amount is 600-3000g/mol.
8. the latex as claimed in one of claims 1-7 comprising polyurethane-modified Carboxy copolymer, wherein described more First alcohol is selected from the pure and mild polyether polyol of polyester polyols that hydroxyl value is 20-200mg KOH/g.
9. the latex according to claim 8 comprising polyurethane-modified Carboxy copolymer, wherein the polyalcohol is selected from hydroxyl Value is the pure and mild polyether polyol of polyester polyols of 50-100mg KOH/g.
10. the latex as claimed in one of claims 1-7 comprising polyurethane-modified Carboxy copolymer, wherein the packet Chain extender containing hydrophilic group be selected from 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid, 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonate, second diamino ethanesulfonic acid sodium and second dihydroxy ethanesulfonic acid sodium.
11. the latex as claimed in one of claims 1-7 comprising polyurethane-modified Carboxy copolymer, wherein the tool Having the monomer of the group and free redical polymerization carbon-carbon double bond that can react with isocyanate group to be selected from has 1-10 carbon atom Glycol with the α of 3-10 carbon atom, the ester of the β-olefinic mono- and/or dicarboxylic acids of unsaturation and its acid anhydrides or with hydroxyl Acrylamide.
12. the latex according to claim 11 comprising polyurethane-modified Carboxy copolymer, wherein it is described have can with it is different The group of cyanic acid ester group reaction and the monomer of free redical polymerization carbon-carbon double bond are selected from (methyl) acrylic acid C2-C6Hydroxyalkyl acrylate, And bis- (the C of N, N-2-C6Hydroxyalkyl) acrylamide.
13. the latex as claimed in one of claims 1-7 comprising polyurethane-modified Carboxy copolymer, wherein the tool Have the monomer of the group and free redical polymerization carbon-carbon double bond that can be reacted with isocyanate group amount be 0.1-5 weight %, with On the basis of the sum of each component weight for preparing polyurethane.
14. the latex according to claim 13 comprising polyurethane-modified Carboxy copolymer, wherein it is described have can with it is different The amount of the monomer of the group and free redical polymerization carbon-carbon double bond of cyanic acid ester group reaction is 0.2-2 weight %, poly- to be used to prepare On the basis of the sum of each component weight of urethane.
15. the latex according to claim 13 comprising polyurethane-modified Carboxy copolymer, wherein it is described have can with it is different The amount of the monomer of the group and free redical polymerization carbon-carbon double bond of cyanic acid ester group reaction is 0.3-1 weight %, poly- to be used to prepare On the basis of the sum of each component weight of urethane.
16. the latex as claimed in one of claims 1-7 comprising polyurethane-modified Carboxy copolymer, wherein the carboxylic Monoethylenically unsaturated carboxylic acid monomeric unit of the base butylbenzene copolymer based on the Carboxy copolymer weight comprising 1-15 weight %.
17. the latex according to claim 16 comprising polyurethane-modified Carboxy copolymer, wherein the Carboxy is total Monoethylenically unsaturated carboxylic acid monomeric unit of the polymers based on the Carboxy copolymer weight comprising 1.5-12 weight %.
18. the latex according to claim 16 comprising polyurethane-modified Carboxy copolymer, wherein the Carboxy is total Monoethylenically unsaturated carboxylic acid monomeric unit of the polymers based on the Carboxy copolymer weight comprising 2-8 weight %.
19. the latex according to claim 16 comprising polyurethane-modified Carboxy copolymer, wherein the monoene category insatiable hunger It is selected from carboxylic acid containing the monoethylenically unsaturated carboxylic acid no more than 10 carbon atoms.
20. the latex according to claim 19 comprising polyurethane-modified Carboxy copolymer, wherein the monoene category insatiable hunger It is selected from carboxylic acid containing the monoethylenically unsaturated carboxylic acid no more than 6 carbon atoms.
21. a kind of glue prepared as defined in any one of claim 1-20 comprising polyurethane-modified Carboxy copolymer The method of cream comprising
A) there is the polyurethane of free redical polymerization carbon-carbon double bond and hydrophilic group by sudden reaction preparation, and
B) in the presence of the polyurethane with free redical polymerization carbon-carbon double bond and hydrophilic group obtained by step a), pass through lotion Polymerization prepares Carboxy copolymer, obtains the latex comprising polyurethane-modified Carboxy copolymer.
22. method according to claim 21, wherein the emulsion polymerization in step b) can be carried out in the case where being added without emulsifier.
23. the latex as defined in any one of claim 1-20 comprising polyurethane-modified Carboxy copolymer is in carpet Purposes in production, building, papermaking, leather, textile printing and dyeing and cement as adhesive.
CN201710038048.5A 2017-01-18 2017-01-18 Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer Active CN106832139B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201710038048.5A CN106832139B (en) 2017-01-18 2017-01-18 Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer
PCT/CN2017/117257 WO2018133610A1 (en) 2017-01-18 2017-12-19 Latex-containing polyurethane-modified carboxyl butadiene-styrene copolymer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710038048.5A CN106832139B (en) 2017-01-18 2017-01-18 Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer

Publications (2)

Publication Number Publication Date
CN106832139A CN106832139A (en) 2017-06-13
CN106832139B true CN106832139B (en) 2019-10-08

Family

ID=59124782

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710038048.5A Active CN106832139B (en) 2017-01-18 2017-01-18 Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer

Country Status (2)

Country Link
CN (1) CN106832139B (en)
WO (1) WO2018133610A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832139B (en) * 2017-01-18 2019-10-08 新辉（中国）新材料有限公司 Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer
JP6965994B2 (en) * 2018-06-25 2021-11-10 Dic株式会社 Aqueous resin composition and its manufacturing method
CN112552452B (en) * 2020-12-09 2022-09-06 珠海金鸡化工有限公司 Modified styrene-butadiene latex and preparation method thereof
CN114181371B (en) * 2022-01-20 2023-11-21 星宇医疗科技股份有限公司 Oil-resistant composite latex and preparation method thereof, and disposable oil-resistant glove and preparation method thereof
CN115057988A (en) * 2022-06-21 2022-09-16 惠州市浩明科技股份有限公司 Thermoplastic elastomer and protective film
CN115232250A (en) * 2022-08-20 2022-10-25 河北昊泽化工有限公司 High-strength styrene-butadiene latex for papermaking coating and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838457A (en) * 2010-05-11 2010-09-22 陕西科技大学 Preparation method of high-solid content crosslinking polyurethane aqueous dispersoid
CN103665311A (en) * 2013-08-22 2014-03-26 常州大学 Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method
CN104072716A (en) * 2014-07-18 2014-10-01 浙江奥康鞋业股份有限公司 Polyurethane elastomer and sole made from same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5721035A (en) * 1996-11-01 1998-02-24 The Goodyear Tire & Rubber Company Foam structure
AU727413B2 (en) * 1997-03-17 2000-12-14 Dow Chemical Company, The Process for preparing carpets having polyurethane backings obtained from polyurethane latex formulations
US20010046581A1 (en) * 2000-01-14 2001-11-29 Shaw Industries, Inc. Carpet with a polymer layer
CN104438026B (en) * 2008-12-22 2018-05-15 陶氏环球技术有限责任公司 Woven carpet coating compound, relevant application method and the product as made from the mixture
CN102731724B (en) * 2012-07-24 2014-07-30 江苏利田科技股份有限公司 Washable anti-aging carboxy styrene-butadiene latex for carpet back coating as well as preparation method and application of latex
KR101722818B1 (en) * 2013-11-18 2017-04-03 주식회사 엘지화학 Carboxylic acid modified-nitrile based copolymer latex composition, preparation method thereof and latex composition for dip-forming comprising the same
CN103755872B (en) * 2013-12-23 2016-08-17 日照广大建筑材料有限公司 The preparation method of drugget carboxylic styrene butadiene latex
CN106832139B (en) * 2017-01-18 2019-10-08 新辉（中国）新材料有限公司 Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838457A (en) * 2010-05-11 2010-09-22 陕西科技大学 Preparation method of high-solid content crosslinking polyurethane aqueous dispersoid
CN103665311A (en) * 2013-08-22 2014-03-26 常州大学 Modified polyurethane/unsaturated polyester resin dibasic alcohol preparation method
CN104072716A (en) * 2014-07-18 2014-10-01 浙江奥康鞋业股份有限公司 Polyurethane elastomer and sole made from same

Also Published As

Publication number Publication date
WO2018133610A1 (en) 2018-07-26
CN106832139A (en) 2017-06-13

Similar Documents

Publication Publication Date Title
CN106832139B (en) Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer
CN106893041A (en) Method for preparing solvent-free aqueous polyurethane dispersion
EP0767185B1 (en) Acrylate copolymer and polymer composition containing the same
TWI773891B (en) Method for preparing waterborne polyurethane dispersion
CA2214470C (en) Nonionic aqueous polyurethane dispersions and processes for making same
EP0660851B1 (en) Polyurethane, use thereof and water paint containing the polyurethane as thickener
CN110317301B (en) Core-shell type polyurethane-acrylic emulsion and preparation method and application thereof
ES2809559T3 (en) Aqueous polymer dispersion for PSAs
JPS61501399A (en) Method for producing polymer polyals
US6566438B1 (en) Hybrid polyurethane-polymer dispersion with high film hardness, method for the production and the use thereof
CN106634548B (en) A kind of polyurethane/acrylate hybridisation emulsion and preparation method thereof
CN104211878A (en) Preparation method of polyurethane epoxy resin acrylate ternary polymerization resin nano aqueous dispersion
TWI718417B (en) Polyurethane with high heat resistance and high scratch resistance and manufacturing method thereof
US6528573B1 (en) Aqueous two-component polyurethane systems with increased impact resistance and good stability properties, method for producing same and their use
US6924336B2 (en) Polymer dispersion comprising particles of polyurethane and a copolymer or terpolymer produced by emulsion polymerization of olefinically unsaturated monomers
US3632789A (en) Production of coatings from olefin copolymers containing hydroxyl groups and polyisocyanates
GB1588797A (en) Process for the production of bead polymers
CN106117451A (en) A kind of preparation method of acrylic ester grafted modified aqueous polyurethane resin
CN105601832B (en) Polyurethane-modified acrylic acid secondary breakup body and preparation method thereof
CN114181353B (en) Synthesis and application of modified waterborne polyurethane composition
TW202003673A (en) Resin composition and synthetic leather
JPH08165318A (en) Production of water-based polyurethane resin
US3472807A (en) Vinyl-containing copolymer latex and method of preparing same
US6197874B1 (en) Polyurethane-polyacrylate hybrid dispersions containing allophanate groups
US6515065B1 (en) Protective colloids

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant