CN109535376A - A kind of preparation method of high-peeling strength waterborne epoxy-polyurethane - Google Patents
A kind of preparation method of high-peeling strength waterborne epoxy-polyurethane Download PDFInfo
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- CN109535376A CN109535376A CN201811464784.8A CN201811464784A CN109535376A CN 109535376 A CN109535376 A CN 109535376A CN 201811464784 A CN201811464784 A CN 201811464784A CN 109535376 A CN109535376 A CN 109535376A
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- polyurethane
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/44—Polycarbonates
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- 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
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- 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
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
- C08G18/6677—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 having at least three hydroxy groups
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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Abstract
The present invention provides a kind of preparation methods of high-peeling strength waterborne epoxy-polyurethane, and specifically, the method obtains waterborne epoxy-polyurethane performed polymer comprising steps of (1) carries out pre-polymerization with polyol masses and diisocyanate cpd；(2) waterborne epoxy-polyurethane lotion is prepared with the waterborne epoxy-polyurethane performed polymer.The coating processes of leather and woven fabric can be widely applied in waterborne epoxy-polyurethane lotion prepared by the method for the present invention, can reduce the discharge of polluted gas and waste water, more adapt to environmentally friendly production policy under the new situation.
Description
Technical field
The invention belongs to environment-friendly water-based polyurethane technical fields, and in particular to a kind of painting for corium and woven fabric base fabric
Cover the preparation method with high-peeling strength waterborne epoxy-polyurethane resin.
Background technique
Process hides final finishing workshop section needs to carry out covering with paint processing to leather surface using a large amount of polyurethane, wherein largely
Roller coating and spraying process.Wherein, spraying process is used in the production of first layer lether, but also with the presence of the more disability in many surfaces more
Scytoblastema needs to carry out recoating decorations by roller coating technology to repair to leather surface, especially for double-layer fur leather sector,
Since double-layer fur does not have grain layer, handled with greater need for by this application pattern.
Currently, ox-hide second layer leather factory generallys use solvent borne polyurethane wet processing to handle scytoblastema surface.
Wherein, used solvent borne polyurethane contains a large amount of DMF, and the precipitation process of DMF needs to cause to prepare using a large amount of water
Generate the waste water containing DMF in the process, pollute the environment, need environmentally friendly technique come it is unfriendly to traditional environment
Technique is substituted.
In conclusion there is an urgent need in the art to provide a kind of conventional solvent type polyurethane that can substitute to excute a law the new work of technique
Skill.
Summary of the invention
The present invention provides a kind of waterborne epoxy-polyurethane resins, with high solids content, high stability, high physical property
And the characteristics of environment friendly, shoe-making industry leather can be met and required.The intensity of upper leather performance common demands surface coating layer
The up to standard of the resistance to tortuous and low-temperature flex resistance energy of room temperature is combined in 80N/3cm or more.In addition this patent preparation is aqueous
Epoxy polyurethane resin field application simple process, integrated artistic flow time are significantly less than wet polyurethane resin.
The first aspect of the present invention, provides a kind of high-peeling strength waterborne epoxy-polyurethane preparation method, and feature exists
In, comprising steps of
(1) pre-polymerization is carried out with polyol masses and diisocyanate cpd, obtains waterborne epoxy-polyurethane performed polymer；Its
In, the pre-polymerization comprising steps of
(1.1) at 80~90 DEG C, it is anti-that first is mixed to form with the polyol masses and diisocyanate cpd
Liquid is answered, carries out reaction 2~3 hours, obtains the first reaction mixture；
(1.2) small molecule chain extender, crosslinking agent and hydrophilic chain extender are added in first reaction mixture, 65
It is reacted 2~4 hours at~85 DEG C, obtains the second reaction mixture；
(1.3) epoxy resin is added in second reaction mixture, it is small that 0.5~1.5 is reacted at 55~70 DEG C
When, obtain waterborne epoxy-polyurethane performed polymer；
Wherein, the polyol masses are polyether polyol or polyester polyol；
And in the reaction solution of the step (i), isocyano in diisocyanate cpd and the polyalcohol and small
The degree of functionality molar ratio of hydroxyl is 1.1~1.8 in molecule chain extender, crosslinking agent and hydrophilic chain extender material；Content of epoxy resin
Account for the 0.5~1.5% of performed polymer gross mass；
(2) waterborne epoxy-polyurethane lotion is prepared with the waterborne epoxy-polyurethane performed polymer, the step is permissible
It is carried out by following (2.1) or (2.2):
(2.1) at 45~65 DEG C, with amine neutralizer and the waterborne epoxy-polyurethane prepolymer reaction 30~120
Second, form waterborne epoxy-polyurethane lotion；Wherein, the second reaction solution degree of neutralization is 80~110%；
(2.2) at 10~20 DEG C, under high speed dispersion state, with the waterborne epoxy-polyurethane performed polymer and go from
Sub- water is emulsified, and waterborne epoxy-polyurethane lotion is obtained.
In another preferred example, before carrying out the pre-polymerization, polyether polyol or polyester polyol are carried out at dehydration
Reason.
In another preferred example, the dehydration is at 105~125 DEG C, in reaction kettle under 0.05~0.08MPa of pressure
It carries out；Or the dehydration carries out in a vacuum drying oven.
In another preferred example, the method also includes steps: after dehydration, by the polyether polyol
Or polyester polyol is cooled to 70~85 DEG C, then carries out prepolymerization reaction.
In another preferred example, in the step (1.2) further include: by the way that organic solvent is added, adjust reaction process
The variation of medium viscosity.
In another preferred example, the step (1.2) carries out in the presence of a catalyst；Preferably, the catalyst
For stannous octoate.
In another preferred example, after the completion of the method further comprises the steps of: preparation, in the waterborne epoxy-polyurethane
Amine chain extender is added in lotion.
In another preferred example, after the method further comprises the steps of: addition amine chain extender, low speed is carried out to lotion and is stirred
It mixes.
In another preferred example, the method further comprises the steps of: having in heating removal waterborne epoxy-polyurethane lotion
Solvent.
In another preferred example, the polyether polyol is selected from the group: polytetrahydrofuran ether 2000, polypropylene glycol
2000, or combinations thereof；And/or
The polyester polyol is selected from the group: polycaprolactone polyol 2000, polycarbonate glycol 2000 or its group
It closes.
In another preferred example, the diisocyanate cpd is selected from the group: toluene di-isocyanate(TDI) (TDI-65),
1, hexamethylene-diisocyanate, or combinations thereof.
In another preferred example, the small molecule chain extender is selected from the group: neopentyl glycol, Isosorbide-5-Nitrae butanediol, 1,6- oneself two
Alcohol, or combinations thereof；And/or
The crosslinking agent is trimethylolpropane；And/or
The hydrophilic chain extender is dihydromethyl propionic acid；And/or
The amine neutralizer is selected from the group: triethylamine, N, N- dimethylethanolamine, or combinations thereof.
In another preferred example, the organic solvent is acetone.
In another preferred example, the epoxy resin in the step (1.3) is E-44.
In another preferred example, the amine chain extender is ethylenediamine.
In another preferred example, in the step (2.2), the additional amount of deionized water be performed polymer total amount 90~
150wt%.
The second aspect of the present invention provides a kind of aqueous polyurethane emulsion, by as described in the first aspect of the invention
Method be prepared.
In another preferred example, the lotion includes one or more features selected from the group below:
Solid content wt%45~50；
Lotion is milky white to translucent；
PH value is 7.0~8.5；
The pot-life is 120~240 days at 15~30 DEG C.
The third aspect of the present invention provides a kind of woven fabric base fabric processing method, the method includes the steps: it will be such as this hair
Aqueous polyurethane emulsion described in bright second aspect is dried after being coated on woven fabric base fabric.
In another preferred example, before the coating, the aqueous polyurethane emulsion is thickened.
In another preferred example, the thickening in the addition waterborne epoxy-polyurethane lotion comprising steps of add
Enter thickener, stirring to suitable roller coating viscosity.
In another preferred example, the coating is roller coating.
In another preferred example, the drying is to be dried using high temperature drying mode.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Specific embodiment
In order to overcome the defect of traditional waterborne polyurethane stripping performance difference in cow leather upper leather and woven fabric upper leather field,
The market competitiveness of conventional urethane is improved, is produced so as to more rapid substitution solvent borne polyurethane and no-solvent type polyurethane
A kind of base fabric coating high-peeling strength waterborne epoxy-polyurethane lotion has been prepared by studying for a long period of time in product, the present inventor.
Present invention employs method of fractional steps synthesis of polyurethane, group needed for introducing step by step, to introduce epoxy resin, improve product
Energy.The coating processes of leather and woven fabric can be widely applied in such waterborne epoxy-polyurethane lotion, can reduce polluted gas and waste water
Discharge, more adapt to environmentally friendly production policy under the new situation.
The preparation of waterborne epoxy-polyurethane
The preparation method of the waterborne epoxy-polyurethane, comprising the following steps:
1) waterborne epoxy-polyurethane performed polymer is prepared
In the preparation of aqueous polyurethane, according to the coating required performance of base fabric, using polyether polyol and/or polyester polyols
Alcohol synthesizes the soft segment of aqueous polyurethane with this as polyalcohol raw material.The polyether polyol is poly- tetrahydro furan
It mutters ether 2000 and/or polypropylene glycol 2000, polyester polyol is polycaprolactone polyol 2000 and/or polycarbonate glycol
2000。
The preparation of base polyurethane prepolymer for use as is carried out using step synthesis, is carried out first to polyether polyol or polyester polyol
High temperature dehydration chooses 105~125 DEG C of lower progress of negative pressure 0.05~0.08 in reaction kettle according to the heatproof attribute of raw material, or
It is carried out dehydrating using vacuum oven.
After dehydration, polyalcohol in reaction kettle is cooled down, temperature is down to 70~85 DEG C.
The type of diisocyanate cpd is selected according to product demand, has selected two kinds of diisocyanate chemical combination
Object.Weigh the diisocyanate cpd of formula design flow, in formula design isocyano and hydroxyl Ratio control 1.1~
1.8；The diisocyanate cpd is preferably toluene di-isocyanate(TDI) (TDI-65) and/or the own diisocyanate of 1.6-
Ester.
Sealing reaction kettle and polyether polyol is added by charging (feeding) equipment for weighed diisocyanate cpd or polyester is more
First alcohol is mixed, it is preferable that can be suitably passed through nitrogen in the process and be protected.
In the first step reaction of pre-polymerization, at 2~3 hours, temperature was controlled at 80~90 DEG C for reaction time control.To the first step
Cool down after reaction, small molecule chain extender, crosslinking agent and hydrophilic chain extender needed for investment reaction carry out chain extension；Preferably,
Small molecule alcohol chain extender can be selected from neopentyl glycol, 1.4 butanediols or 1.6- hexylene glycol, and crosslinking agent can be trihydroxy methyl third
Alkane, hydrophilic chain extender can be dihydromethyl propionic acid.
Chain extender collocation mode can be adjusted according to properties of product.In the preferred embodiment, according to chain extender and
The reactivity of diisocyanate cpd determines additional amount and the addition time of catalyst, while according to different in reaction process
The variation of cyanic acid ester content carries out the adjustment of time and temperature.Preferably, at 2~4 hours, temperature control existed for reaction time control
65~85 DEG C.
In the second step reaction process of pre-polymerization, organic solvent is can be used to be adjusted in the variation of viscosity, anti-to make with this
Carrying out of answering is easier to manipulate.Preferably, the organic solvent is acetone.
After reaction to second step, high-purity epoxy resin is added in cooling, and the reaction time controlled at 0.5~1.5 hour,
Temperature is controlled at 55~70 DEG C, reacts and waterborne epoxy-polyurethane performed polymer is made.The epoxy resin can be high-purity ring
Oxygen resin E-44.
2) waterborne epoxy-polyurethane lotion is prepared
Base polyurethane prepolymer for use as is prepared into polyaminoester emulsion using emulsifying manner, emulsifying manner may include following methods
(2.1) or (2.2):
(2.1) control of pre-polymerization temperature carries out emulsion process at 45~65 DEG C, uses in two kinds of amines in emulsion process
Reacted with agent with the hydrophilic chain extension group in performed polymer, degree of neutralization control 80~110%, reaction time control 30~
120 seconds.The amine neutralizer is preferably triethylamine and/or N, N- dimethylethanolamine.
(2.2) preparing water used in polyaminoester emulsion is deionized water, and temperature is controlled at 10~20 DEG C.Emulsion process is in high speed
It is carried out under dispersity, a kind of amine chain extender is added after emulsion inverse is complete, to keep stability of emulsion.Preferably, institute
The amine chain extender stated is ethylenediamine.
Before lotion storage or delivery, the organic solvent in removal waterborne epoxy-polyurethane lotion can also be optionally heated,
Ensure water-based lotion.
For the aqueous polyurethane emulsion solid content being prepared 45%~50%, lotion is milky white to translucent, cream
Liquid pH value is 7.0~8.5.The aqueous polyurethane emulsion of preparation can be saved in 15~30 DEG C, with this condition, the pot-life
120~240 days.
Compared with prior art, the invention has the advantages that
1, high solids content.The existing universal solid content of aqueous polyurethane is relatively low, and the lower aqueous polyurethane of solid content causes
Production efficiency reduces, and production product storage occupancy stock area is larger, improves production cost and the storage of polyurethane production producer
It is saved as this, from the competitiveness for most fundamentally reducing product.In addition same traffic condition can not transport identical effective component,
Lead to the increase of transportation cost.Furthermore in the use process of product, it is unable to satisfy in the service performance of common water borne polyurethane
Client produces the demand of premium quality product, and performance can not mutually be equal to solvent borne polyurethane product, influences the scope of application of product.
For large arch dam aqueous polyurethane closer to solvent borne polyurethane in performance, the application of large arch dam polyurethane can greatly shorten base
Cloth coats the drying time after polyurethane, reduces production cost, to make the aqueous polyurethane product of large arch dam with more market
Competitiveness.
2, high stability.Compared with traditional waterborne polyurethane resin, the introducing of epoxy resin can make entire aqueous poly- ammonia
Ester system is more stable.Epoxy resin is introduced by the way of graft copolymerization, and the chemical property of entire strand can be made to increase,
For blending method, stability, physical and chemical properties can be dramatically increased.
3, high physical property.After waterborne epoxy-polyurethane resin is coated on base fabric, it can make scrim surfaces layer that there is high stripping
From intensity, the basic demand under existing light industry standard for base fabric physical property can satisfy completely.And then base fabric can be expanded
The use scope of product produces the product for the person's demand that more meets Modern consumer.
4, environment friendly.In the production process of waterborne epoxy-polyurethane resin, the generation of no high pollution waste water, low VOC
It is non-hazardous safely to the health of human body of Workshop Production operator with low risky operation.In the application coating procedure of product
Characteristic with safety easy to operate and without volatilizable organic compound, and it is useless to generate the pollution containing organic solvent
Water has apparent environmentally friendly advantage compared to product used in existing leather and synthetic leather enterprise.It can be from whole
The exhaust gas and cost of sewage disposal that enterprise is reduced on body, make enterprise can satisfy the requirement of national environmental protection, reduce the environmental protection of enterprise
Produce pressure.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Embodiment 1
Step 1: waterborne epoxy-polyurethane performed polymer is prepared
It chooses polyether polyol-polytetrahydrofuran ether 2000 and is used as polyalcohol raw material, weighing quality is 300kg, to poly-
Ethoxylated polyhydric alcohol carries out high temperature dehydration, and 110 DEG C of temperature carry out under pressure 0.05MPa in reaction kettle, and dewatering time 2 hours.Dehydration
Temperature is down to 85 DEG C after the completion.Diisocyanate cpd toluene di-isocyanate(TDI) 85kg is weighed, is added by charging (feeding) equipment close
Reaction kettle is sealed, nitrogen is passed through and is protected.Start the first step reaction of pre-polymerization, reaction time control is 2 hours, and temperature control exists
82℃.Cool down after reaction to the first step, puts into small molecule chain extender neopentyl glycol 0.8kg, crosslinking agent trimethylolpropane
0.8kg, hydrophilic chain extender dihydromethyl propionic acid 18kg carry out chain extension, and reaction temperature is 80 DEG C.It is weighed after reacting and carrying out 1 hour
The addition of 90g stannous octoate catalyst, while 30kg acetone is added, test reaction object after the reaction was continued 2 hours, 2 hours
The content of middle isocyanates, remaining isocyano amount are less than the 40% of additional amount, stop second step reaction.It reacts and ties to second step
5kg epoxy resin E44 is added in Shu Hou, cooling, and reaction temperature is 70 DEG C, and the reaction time controlled at 0.5 hour.Third step reaction knot
Waterborne epoxy-polyurethane performed polymer is obtained after beam.
Step 2: waterborne epoxy-polyurethane lotion is prepared
Base polyurethane prepolymer for use as made from step 1 is cooled to 65 DEG C to emulsify, amine neutralizer is used in emulsion process
N, N- dimethylethanolamine are reacted with the hydrophilic chain extension group in performed polymer, degree of neutralization 80%, and reaction time control exists
30 seconds.Deionized water temperature is controlled at 10 DEG C, and deionized water 580kg is added under high speed dispersion state.After emulsion inverse is complete
Amine chain extender ethylenediamine 4kg is added, stirs at low speed 0.5 hour.Lotion is pumped into distillation still heating stirring under negative pressure state
0.5 hour, the acetone in lotion is removed, lotion storage is released after cooling.It is 45% that aqueous polyurethane emulsion solid content, which is made, cream
Liquid is milky white state, ph value of emulsion 7.5.
Step 3: the application of waterborne epoxy-polyurethane lotion
Step 2 waterborne epoxy-polyurethane lotion is thickened using aqueous high shear polyurethane resin of thickening, thickening is adopted
It is carried out with agitating mode, thickener is added in waterborne epoxy-polyurethane lotion and is thickened to suitable roller coating viscosity, using roll coating model
It coated on woven fabric base fabric, is dried by the way of high temperature drying, the test of peel strength, removing is carried out after cooling to be dried
Intensity is 100N/3cm, complies fully with the removing requirement of substrate.
Embodiment 2
Step 1: waterborne epoxy-polyurethane performed polymer is prepared
It chooses polyether polyol-polypropylene glycol 2000 and polycarbonate glycol 2000 and is used as polyalcohol raw material, poly- the third two
It is 100kg that alcohol 2000, which weighs quality, and it is 260kg that polycarbonate glycol 2000, which weighs quality,.It is de- that high temperature is carried out to polyether polyol
Water, 100 DEG C of temperature carry out under pressure 0.08MPa in reaction kettle, and dewatering time 1.5 hours.Temperature is down to 80 after the completion of dehydration
℃.Diisocyanate cpd toluene di-isocyanate(TDI) 95kg and 1.6- hexamethylene diisocyanate 10kg is weighed, charging (feeding) equipment is passed through
Sealing reaction kettle is added, is passed through nitrogen and is protected.Start the first step reaction of pre-polymerization, reaction time control is 2.5 hours, temperature
Degree control is at 88 DEG C.Cool down after reaction to the first step, puts into small molecule chain extender neopentyl glycol 1.5kg and 1.4 butanediols
1.2kg, hydrophilic chain extender dihydromethyl propionic acid 22kg carry out chain extension, and reaction temperature is 85 DEG C.It is weighed after reacting and carrying out 1 hour
The addition of 100g stannous octoate catalyst, while 20kg acetone is added, test reaction after the reaction was continued 1.5 hours, 2 hours
The content of isocyanates in object, remaining isocyano amount are less than the 40% of additional amount, stop second step reaction.It is reacted to second step
After, 6kg epoxy resin E44 is added in cooling, and reaction temperature is 60 DEG C, and the reaction time controlled at 1 hour.Third step reaction knot
Waterborne epoxy-polyurethane performed polymer is obtained after beam.
Step 2: waterborne epoxy-polyurethane lotion is prepared
Base polyurethane prepolymer for use as made from step 1 is cooled to 60 DEG C to emulsify, amine neutralizer is used in emulsion process
N, N- dimethylethanolamine are reacted with the hydrophilic chain extension group in performed polymer, degree of neutralization 90%, and reaction time control exists
30 seconds.Deionized water temperature is controlled at 10 DEG C, and deionized water 510kg is added under high speed dispersion state.After emulsion inverse is complete
Amine chain extender ethylenediamine 2kg is added, stirs at low speed 1 hour.Heating stirring 1 under negative pressure state in lotion suction distillation still is small
When, the acetone in lotion is removed, lotion storage is released after cooling.It is 50% that aqueous polyurethane emulsion solid content, which is made, and lotion is
Milky white state, ph value of emulsion 7.8.
Step 2 waterborne epoxy-polyurethane lotion is thickened, woven fabric base fabric is coated on using roll coating model, using height
The mode of temperature drying is dried, and the test of peel strength is carried out after cooling to be dried, and the peel strength tested meets base
The removing requirement of material.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of high-peeling strength waterborne epoxy-polyurethane preparation method, which is characterized in that comprising steps of
(1) pre-polymerization is carried out with polyol masses and diisocyanate cpd, obtains waterborne epoxy-polyurethane performed polymer；Wherein,
The pre-polymerization comprising steps of
(1.1) at 80~90 DEG C, it is mixed to form the first reaction solution with the polyol masses and diisocyanate cpd,
It carries out reaction 2~3 hours, obtains the first reaction mixture；
(1.2) small molecule chain extender, crosslinking agent and hydrophilic chain extender are added in first reaction mixture, 65~85
It is reacted 2~4 hours at DEG C, obtains the second reaction mixture；
(1.3) epoxy resin is added in second reaction mixture, reacts 0.5~1.5 hour, obtains at 55~70 DEG C
To waterborne epoxy-polyurethane performed polymer；
Wherein, the polyol masses are polyether polyol or polyester polyol；
Isocyano and the polyalcohol and small molecule and in the reaction solution of the step (i), in diisocyanate cpd
The molar ratio of chain extender, crosslinking agent and the hydroxyl in hydrophilic chain extender material is 1.1~1.8；Content of epoxy resin accounts for performed polymer
0.5~1.5wt% of gross mass；
(2) waterborne epoxy-polyurethane lotion is prepared with the waterborne epoxy-polyurethane performed polymer, the step can pass through
(2.1) or (2.2) carry out below:
(2.1) at 45~65 DEG C, with amine neutralizer and described waterborne epoxy-polyurethane prepolymer reaction 30~120 seconds,
Form waterborne epoxy-polyurethane lotion；Wherein, the second reaction solution degree of neutralization is 80~110%；
(2.2) at 10~20 DEG C, under high speed dispersion state, with the waterborne epoxy-polyurethane performed polymer and deionized water
It is emulsified, obtains waterborne epoxy-polyurethane lotion.
2. the method as described in claim 1, which is characterized in that the method further include: right before carrying out the pre-polymerization
Polyether polyol or polyester polyol are carried out dehydrating；The dehydration is at 105~125 DEG C, the negative pressure in reaction kettle
It is carried out under 0.05~0.08atm；Or the dehydration carries out in a vacuum drying oven.
3. the method as described in claim 1, which is characterized in that after the completion of the method further comprises the steps of: preparation, described
Waterborne epoxy-polyurethane lotion in amine chain extender is added.
4. the method as described in claim 1, which is characterized in that the method further comprises the steps of: heating removal water-base epoxy
Organic solvent in polyaminoester emulsion.
5. the method as described in claim 1, which is characterized in that the polyether polyol is selected from the group: polytetrahydrofuran ether
2000, polypropylene glycol 2000, or combinations thereof；And/or
The polyester polyol is selected from the group: polycaprolactone polyol 2000, polycarbonate glycol 2000, or combinations thereof.
6. the method as described in claim 1, which is characterized in that the diisocyanate cpd is selected from the group: toluene two
Isocyanates (TDI-65), 1, hexamethylene-diisocyanate, or combinations thereof.
7. the method as described in claim 1, which is characterized in that the small molecule chain extender is selected from the group: neopentyl glycol, 1,
4 butanediols, 1,6- hexylene glycol, or combinations thereof；And/or
The crosslinking agent is trimethylolpropane；And/or
The hydrophilic chain extender is dihydromethyl propionic acid；And/or
The amine neutralizer is selected from the group: triethylamine, N, N- dimethylethanolamine, or combinations thereof.
8. preparation method as described in claim 1, which is characterized in that the epoxy resin in the step (1.3) is E-44.
9. a kind of aqueous polyurethane emulsion, which is characterized in that be prepared by method a method as claimed in any one of claims 1-8.
10. a kind of woven fabric base fabric processing method, which is characterized in that comprising steps of by aqueous polyurethane as claimed in claim 9
Lotion is dried after being coated on woven fabric base fabric.
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| CN117626677A (en) * | 2024-01-25 | 2024-03-01 | 浙江梅盛新材料有限公司 | High-peel-strength renewable antibacterial aqueous polyurethane synthetic leather and preparation method thereof |
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