CN107778439A - A kind of aqueous polyurethane is from matting resin preparation method - Google Patents

A kind of aqueous polyurethane is from matting resin preparation method Download PDF

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Publication number
CN107778439A
CN107778439A CN201711061259.7A CN201711061259A CN107778439A CN 107778439 A CN107778439 A CN 107778439A CN 201711061259 A CN201711061259 A CN 201711061259A CN 107778439 A CN107778439 A CN 107778439A
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CN
China
Prior art keywords
parts
acetone
aqueous polyurethane
sulfonic acid
minutes
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Withdrawn
Application number
CN201711061259.7A
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Chinese (zh)
Inventor
应建忠
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Yongjia Xincheng Technology Service Co Ltd
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Yongjia Xincheng Technology Service Co Ltd
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Priority to CN201711061259.7A priority Critical patent/CN107778439A/en
Publication of CN107778439A publication Critical patent/CN107778439A/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—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
    • C08G18/6666—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
    • C08G18/70—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings

Abstract

The present invention relates to a kind of aqueous polyurethane from matting resin preparation method, by polytetramethylene ether diol, cycloalkyl aliphatic diisocyanate, IPDI or 4, one or two kinds of mixtures of 4' dicyclohexyl methyl hydride diisocyanates, diamino sulfonic acid salt, aqueous polyurethane association thickener, catalyst, deionized water, 1, 4 butanediols or 1, the mixture of one or both of 6 hexylene glycols, diamino sulfonic acid salt is 2 [(2 aminoethyl) amino] ethyl sulfonic acid sodium, at least two secondary amine class chain extenders and hydrazine hydrate, Molecular Design is reached using stepwise reaction, prepare the waterborne polyurethane resin particle of " soft core duricrust " structure, form a kind of special hollow microsphere structure；Good with emulsion stability, emulsification technology requires low, the advantages that product stability is good, and extinction effect is good.

Description

A kind of aqueous polyurethane is from matting resin preparation method
Technical field
The invention belongs to polymeric material field, the preparation method especially with respect to a kind of aqueous polyurethane from matting resin. The present invention is applied to the finishing agent of leather and synthetic leather.
Background technology
At present, the domestic preparation method for waterborne polyurethane coating agent matting resin is broadly divided into two kinds：One is water Water-based delustring filler, such as aerosil are added on the basis of property polyurethane finishing agent, by solid particle for light Diffusing reflection caused by extinction effect reach final purpose；It is another then be a kind of special molecular structure of design or emulsion Grain, in the drying process because water-soluble effect occurs during this for the change of particle shape, and different groups, is produced coarse Surface reaches the extinction effect of film.If number of patent application is CN201110404622.7 " the water-based poly- ammonia of extinction type use for synthetic leather Ester finishing agent ", by adding 1%-10% flatting silica, i.e. aerosil, to reach the effect of delustring.It is prepared by this mode Matting resin, its major defect is stability deficiency, the requirement of emulsion particle diameter distribution uniformity is compared during the manufacturing Height, precipitation is easily produced when storing for a long time.The a kind of of application number CN201510386759.2 is reacted from the water-based poly- ammonia of extinction type Ester resin and preparation method and application, by tetrahydrofuran ether and isocyanate polymeric, by dihydroxymethyl into the base after salt Group is emulsified, and using 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium and hydrazine hydrate as rear chain extender, preparing one kind has spherical junctions The aqueous polyurethane emulsion of structure.The latex particle of this spherical structure can keep its spheroid form very well in the drying process, Its extinction effect is determined by the dosage of hydrazine hydrate.Its shortcoming is that the rigidity of latex particle in itself is inadequate, emulsification, rear chain extension with And dry during easily because acetone, moisture content volatilize etc. caused by microstress and cause the deformation of spheric granules, so as to cause to disappear Light effect fails, or even ultimately forms the film of high glaze.Moreover, emulsification of this technology of preparing for performed polymer requires pole Height, produce poor repeatability, industrialized quality stability deficiency.
The content of the invention
Present invention the shortcomings that existing for prior art, the structure of resin in itself is improved, prepare that " soft core is hard The waterborne polyurethane resin particle of shell " structure, a kind of special hollow microsphere structure is formed, and ensure that this structure is done in emulsion It is dry, there is good stability, and the technology to emulsification procedure is reduced in preparation process is produced especially during heated drying It is required that make it have good industrialization reproducibility, and the good aqueous polyurethane of extinction effect is from matting resin preparation method.
Technical scheme, by polytetramethylene ether diol, cycloalkyl aliphatic diisocyanate, isophorone two It is one or two kinds of mixtures of isocyanates or 4,4'- dicyclohexyl methyl hydride diisocyanates, diamino sulfonic acid salt, water-based poly- The mixing of one or both of urethane association thickener, catalyst, deionized water, BDO or 1,6- hexylene glycol Thing, diamino sulfonic acid salt are 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium, at least two secondary amine class chain extenders and hydrazine hydrate, are adopted Reach Molecular Design with stepwise reaction；Mainly each material uses following dispensing ratio and processing step：
1) feed intake polytetramethylene ether diol, and 2000,800 parts of molecular weight enters 6000L reactors, is warming up to 1150C, take out true Sky dehydration 0.5 hour, opens reflux condensation mode valve, is passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 100 parts of butanone that feed intake, 222.4 parts of 4,4'- dicyclohexyl methyl hydride diisocyanates, 0.6 part of catalyst enters above reactor, reacts 1.5 hours；
3）Feed intake 18 parts 400 parts of butanone, small point of aliphatic of chain extender enters above reactor, and 800C continues reaction 2.0 hours；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；At dispersion impeller edge, linear velocity is Under more than 12m/s high speed shears, 2- [(2- aminoethyls) amino] 46.4 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao are rapidly joined Speed stirring 30 minutes；Continued that 600 parts of acetone are at the uniform velocity added dropwise in 30 minutes, to keep viscosity when reacting；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine chain extenders and acetone in advance, put into reactor under high velocity agitation, and instead Answer 5 minutes；
6）Rapidly join 2440 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 3 parts of hydrazine hydrate and the mixture of 27 parts of deionized water in advance, once put into above reactor, high speed shear 5 is divided Clock；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to requiring Value；
10）Solid content is adjusted using deionized water, and viscosity is adjusted with 20 parts of aqueous polyurethane association thickeners, can be added few Substrate wetting agents or levelling agent 0.2-0.5 parts are measured, after qualified after testing, is packed by packaging instruction with 80 mesh filter screen filtrations.
The present invention compared with prior art the advantages of be：Using Molecular Design and latex particle structure design, prepare Go out the waterborne polyurethane resin particle of " soft core duricrust " structure, form a kind of special hollow microsphere structure, abandoned water-based The way of flatting silica is added in polyaminoester emulsion, reaches more more excellent from extinction effect than addition flatting silica, avoids addition Flatting silica causes the negative effects such as emulsion unstability；Good with emulsion stability, emulsification technology requires low, and product is stable The advantages that property is good, and extinction effect is good.
Embodiment
The aqueous polyurethane of the present invention is different by polytetramethylene ether diol, cycloalkyl aliphatic two from matting resin preparation method Cyanate, one or two kinds of mixtures of IPDI or 4,4'- dicyclohexyl methyl hydride diisocyanates, two In sulfamate, aqueous polyurethane association thickener, catalyst, deionized water, BDO or 1,6- hexylene glycol Mixture, the diamino sulfonic acid salt of one or two are 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium, the expansion of at least two secondary amine classes Chain agent and hydrazine hydrate, Molecular Design is reached using stepwise reaction；It is characterized in that each material using following dispensing ratio and Processing step：
1) feed intake polytetramethylene ether diol, and 2000,800 parts of molecular weight enters 6000L reactors, is warming up to 1150C, take out true Sky dehydration 0.5 hour, opens reflux condensation mode valve, is passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 100 parts of butanone that feed intake, 222.4 parts of 4,4'- dicyclohexyl methyl hydride diisocyanates, 0.6 part of catalyst enters above reactor, reacts 1.5 hours；
3）Feed intake 18 parts 400 parts of butanone, small point of aliphatic of chain extender enters above reactor, and 800C continues reaction 2.0 hours；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；At dispersion impeller edge, linear velocity is Under more than 12m/s high speed shears, 2- [(2- aminoethyls) amino] 46.4 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao are rapidly joined Speed stirring 30 minutes；Continued that 600 parts of acetone are at the uniform velocity added dropwise in 30 minutes, to keep viscosity when reacting；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine chain extenders and acetone in advance, put into reactor under high velocity agitation, and instead Answer 5 minutes；
6）Rapidly join 2440 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 3 parts of hydrazine hydrate and the mixture of 27 parts of deionized water in advance, once put into above reactor, high speed shear 5 is divided Clock；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to requiring Value；
10）Solid content is adjusted using deionized water, and viscosity is adjusted with 20 parts of aqueous polyurethane association thickeners, can be added few Substrate wetting agents or levelling agent 0.2-0.5 parts are measured, after qualified after testing, is packed by packaging instruction with 80 mesh filter screen filtrations.
The present invention uses carbon number to carry out chain extension in the course of the polymerization process for more than 4 small molecule glycol, use not same amount Chain extender control the purpose of different molecular weight to reach, and the design of different molecular weight will also influence latex particle inside points Swelling action inside son amount size and latex particle with solvent or water, so as to influence latex particle size and in the drying process Particle rigidly maintain ability；
In Molecular Design, a free cycloalkanes group diisocyanate is linked together with hydrophilic radical, with enhancing The link strength and rigidity of latex particle hydrophilic radical annex, to reach the purpose for strengthening latex particle rigidity；
Using strand closed loop configuration, the part being connected with Diamines chain extender is the soft core part of long chain, with sulfonate Connected part is duricrust part；After frozen water emulsifies, outwardly, soft core part inwardly, is formed soft latex particle hydrophilic segment Core monocoque；
Controlled by the molecular weight of small molecule glycol, and the combination of different isocyanate groups and the control of amount, in chain extension process The middle segment for forming different rigidity, to reach the purpose of Molecular Design；In moisture content volatilization process, soft core monocoque and Between the polar molecule formed between sulfonate and other groups or intramolecular active force and hydrogen bond etc. can effectively ensure that latex Grain maintains certain spherical state and indeformable, is finally reached the diffusing reflection effect of particle surface；
Closed loop is carried out using diamine chain stretching agent chain extension before emulsification, remaining remaining isocyanate group passes through hydrazine hydrate after emulsification Short chain groups carry out chain conjunction, and the effect of hydrogen bond, and big latex particle effectively is carried out into microballoon, further forms rigidization Particle, strengthen final extinction effect；
Sulfamic acid sodium salt is used as unique emulsifying agent（Hydrophilic chain extender）, effectively improve prior art and use carboxylate As emulsifying agent, hydrophilic radical forms the problem of being swelled in organic solvent and water, ensures latex particle rigid structure and inside Hydrophobic microscopic pattern is formed, spherical rigid structure is kept in the drying process and indeformable, there is good stability.
The present invention reaches the purpose of Molecular Design using stepwise reaction：
The first step is reacted, is the reaction of polyalcohol and isocyanates, 2mol polyalcohol and 5moL's is different under catalyst action Polyisocyanate reactant, generate 2mol end isocyano macromolecular, and remaining 1mol isocyanates.
Second step is reacted, is first time chain extending reaction.Add 1mol small molecule polyols, such as BDO, generation Macromolecular after 1mol chain extension, and the end isocyano macromolecular of remaining 1mol reaction first step generations.
The 3rd step is reacted, is entered for 1mol reaction second step product of 2- [(2- aminoethyls) amino] the ethyl sulfonic acid sodium to 2mol Row 1：2 chain extensions, molecular weight, which increases, to be twice.Meanwhile 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium is also hydrophilic chain extender, this step All strand groups are all connected on hydrophilic radical.
The 4th step is reacted, the diamine chain stretching agent for being 1mol carries out 1 to the product for reacting the 3rd step：2 chain extensions, while by long point Subchain carries out closed loop.After frozen water emulsification is added, hydrophilic radical is in the periphery of latex particle, because the relation of structure, sulfonate The hydrophilic radical of formation is larger, and hydrophobic long chain is in the inside of latex particle, so as to form the breast of " soft core duricrust " Plastic structure.The latex particle of this structure, there is the stability of good storage stability and different PH scope, and dry During dry, because in the presence of molecular rigidity and intramolecule and outside hydrogen bond, with the volatilization of moisture content, latex particle maintains Rigid structure it is very capable, it is not easy to because moisture content volatilization and cause particle deformation, it is right so as to form coarse film surface Light forms good diffusing reflection effect.
The latex particle for the stabilization that the Molecular Design of the present invention is formed, and the rule of latex particle particle diameter distribution Property, the manufacture for the aqueous polyurethane particle of hollow microsphere structure provides a kind of new thinking.
The injected volume " part " of each material is a mass unit in preparation method of the present invention, typically uses 1Kg as a matter Unit is measured, the injected volume of each material can increase and decrease in proportion according to reactor capacity or batch size, each material in the present embodiment Amount is than being relative preferred values with the reaction time.

Claims (1)

1. a kind of aqueous polyurethane is from matting resin preparation method, it is characterized in that：
1) feed intake polytetramethylene ether diol, and 2000,800 parts of molecular weight enters 6000L reactors, is warming up to 1150C, vacuumize Dehydration 0.5 hour, reflux condensation mode valve is opened, be passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 100 parts of butanone that feed intake, 222.4 parts of 4,4'- dicyclohexyl methyl hydride diisocyanates, 0.6 part of catalyst enters above reactor, reacts 1.5 hours；
3）Feed intake 18 parts 400 parts of butanone, small point of aliphatic of chain extender enters above reactor, and 800C continues reaction 2.0 hours；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；At dispersion impeller edge, linear velocity is Under more than 12m/s high speed shears, 2- [(2- aminoethyls) amino] 46.4 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao are rapidly joined Speed stirring 30 minutes；Continued that 600 parts of acetone are at the uniform velocity added dropwise in 30 minutes, to keep viscosity when reacting；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine chain extenders and acetone in advance, put into reactor under high velocity agitation, and instead Answer 5 minutes；
6）Rapidly join 2440 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 3 parts of hydrazine hydrate and the mixture of 27 parts of deionized water in advance, once put into above reactor, high speed shear 5 is divided Clock；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to required value；
10）Solid content is adjusted using deionized water, and viscosity is adjusted with 20 parts of aqueous polyurethane association thickeners, can be added few Substrate wetting agents or levelling agent 0.2-0.5 parts are measured, after qualified after testing, is packed by packaging instruction with 80 mesh filter screen filtrations.
CN201711061259.7A 2017-11-02 2017-11-02 A kind of aqueous polyurethane is from matting resin preparation method Withdrawn CN107778439A (en)

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Application Number Priority Date Filing Date Title
CN201711061259.7A CN107778439A (en) 2017-11-02 2017-11-02 A kind of aqueous polyurethane is from matting resin preparation method

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108794723A (en) * 2018-04-23 2018-11-13 合肥科天水性科技有限责任公司 A kind of biology base dumb light aqueous polyurethane dispersion and preparation method thereof
CN108997559A (en) * 2018-06-07 2018-12-14 安徽匠星联创新材料科技有限公司 A kind of dumb light type water-base polyurethane material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108794723A (en) * 2018-04-23 2018-11-13 合肥科天水性科技有限责任公司 A kind of biology base dumb light aqueous polyurethane dispersion and preparation method thereof
CN108997559A (en) * 2018-06-07 2018-12-14 安徽匠星联创新材料科技有限公司 A kind of dumb light type water-base polyurethane material and preparation method thereof

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Application publication date: 20180309