CN110093138A - A kind of color inhibition high-strength polyurethane U.S. seam glue and preparation method thereof - Google Patents

A kind of color inhibition high-strength polyurethane U.S. seam glue and preparation method thereof Download PDF

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Publication number
CN110093138A
CN110093138A CN201910452931.8A CN201910452931A CN110093138A CN 110093138 A CN110093138 A CN 110093138A CN 201910452931 A CN201910452931 A CN 201910452931A CN 110093138 A CN110093138 A CN 110093138A
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China
Prior art keywords
molecular sieve
color inhibition
polyurethane
inhibition high
strength polyurethane
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Chinese (zh)
Inventor
徐承友
李桂妃
詹锋
张志文
周传军
谢志明
任如飞
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Guangdong Shengye Chemical Technology Co Ltd
Guangdong Pustar Sealing Adhesive Co Ltd
Original Assignee
Guangdong Shengye Chemical Technology Co Ltd
Guangdong Pustar Sealing Adhesive Co Ltd
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Application filed by Guangdong Shengye Chemical Technology Co Ltd, Guangdong Pustar Sealing Adhesive Co Ltd filed Critical Guangdong Shengye Chemical Technology Co Ltd
Priority to CN201910452931.8A priority Critical patent/CN110093138A/en
Publication of CN110093138A publication Critical patent/CN110093138A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three 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
    • C08G18/65—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
    • C08G18/70—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The present invention provides a kind of color inhibition high-strength polyurethane U.S. seam glue and preparation method thereof, and the U.S. seam glue is made of the component of following mass percent: base polyurethane prepolymer for use as 20~60%, plasticizer 0~10%, reinforced filling 30~60%, modified molecular screen 2~5%, catalyst 0.02~1%, antioxidant 0.1~1%, light stabilizer 0.1~1%, mould inhibitor 0.5~3%, deicer 0.5~1%；The viscosity of the base polyurethane prepolymer for use as is 10000~15000mp.s；Wherein, the modified molecular screen is made of the component of following mass percent: molecular sieve activation powder 40~80%, curing agent 20~60%；The molecular sieve is 5A activated molecular sieve and/or 13X activated molecular sieve, and the curing agent is small molecule aliphatic diamine, and the molecular weight of the small molecule aliphatic diamine is 80~250.Color inhibition high-strength polyurethane U.S. seam glue provided by the invention has the characteristics that intensity is high, adhesive property is excellent, be not easy xanthochromia and fungicidal properties is good.

Description

A kind of color inhibition high-strength polyurethane U.S. seam glue and preparation method thereof
Technical field
The present invention relates to sealant technical field, more particularly, to a kind of color inhibition high-strength polyurethane beauty stitch glue and Preparation method.
Background technique
Family kitchen and bath decorates since long-time is by the effect of water stain, greasy dirt and mould, it is contemplated that durability and aesthetics, it is right Water-fast, the resistance to greasy dirt of product, scratch resistance scrape along fungus resistance can have high requirements.Currently, family kitchen and bath fits up and uses glue in the market Type it is more, application relatively widely mainly has a bi-component epoxy.Its fungus resistance can be good, and intensity is high, but exists and apply Work trouble, the shortcomings that poor water resistance, easy xanthochromia, especially easy xanthochromia the problem of, in light color, high whiteness top grade kitchen tools, sanitary ware It is difficult in gap sealing.
Therefore, it is necessary to which to provide a kind of color inhibition, water resistance good, adhesive property is excellent, construction is simple and mildew resistance Polyurethane beauty that can be good stitches glue.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of color inhibition high-strength polyurethane beauty to stitch glue, Color inhibition high-strength polyurethane U.S. seam glue provided by the invention is high with intensity, adhesive property is excellent, is not easy xanthochromia and mildew resistance The good feature of energy.
Another object of the present invention is to provide the preparation methods of above-mentioned color inhibition high-strength polyurethane U.S. seam glue.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of color inhibition high-strength polyurethane U.S. seam glue, the U.S. seam glue are made of the component of following mass percent:
Base polyurethane prepolymer for use as 20~60%, plasticizer 0~10%, reinforced filling 30~60%, modified molecular screen 2~5%, Catalyst 0.02~1%, antioxidant 0.1~1%, light stabilizer 0.1~1%, mould inhibitor 0.5~3%, deicer 0.5~ 1%；The viscosity of the base polyurethane prepolymer for use as is 10000~15000mp.s；
Wherein, the modified molecular screen is made of the component of following mass percent:
Molecular sieve activation powder 40~80%, curing agent 20~60%；The molecular sieve is 5A activated molecular sieve and/or 13X Activated molecular sieve, the curing agent are small molecule aliphatic diamine, the molecular weight of the small molecule aliphatic diamine is 80~ 250。
In the present invention, by the modified obtained modified molecular screen of molecular sieve activation powder small molecule aliphatic diamine with it is other Component mixes, and a kind of polyurethane U.S. seam glue of one-component has been prepared.Beauty provided by the invention stitches glue for curing agent Keep apart the storage stability that ensure that entire component with base polyurethane prepolymer for use as, when use squeezes out glue, molecular sieve adsorbed moisture To displace small molecule aliphatic diamine curing agent, solidifies it with base polyurethane prepolymer for use as cross-linking reaction and generate urea bond, solidification Speed is fast, rapid reaction and not blistering, the polyurethane U.S. seam glue intensity with higher that is prepared, color inhibition excellent effect, Also there is preferable scratch resistance and stronger mildew-proof function, be particularly suitable for family's use and be particularly suitable for kitchen and bath's decoration.
Preferably, in the modified molecular screen, the mass ratio of molecular sieve activation powder and curing agent be 0.4~0.8:0.2~ 0.6。
Preferably, in the modified molecular screen, the mass ratio of molecular sieve activation powder and curing agent is 0.55~0.75:0.25 ~0.45.
Preferably, the modified molecular screen the preparation method is as follows:
By the dry water removal of molecular sieve activation dried bean noodles, placement for 24 hours or more is then mixed with curing agent, finally air-dries molecular sieve surface To remove the curing agent of surface attachment to get the modified molecular screen.
It is further preferable that the modified molecular screen the preparation method is as follows:
Molecular sieve activation powder is placed in Muffle furnace after 300 DEG C of baking 6h slightly cooling be placed in drying tower and is cooled to room Temperature, modifying agent are shifted after being removed water with 3A molecular sieve and are sealed, and suitable molecular sieve activation powder is added in modifying agent and places For 24 hours, it takes out the vacuum under room temperature environment and air-dries surface to get modified molecular screen.
Preferably, the small molecule aliphatic diamine is 1,3- cyclohexane diamine, 1,3- diamine hexahydrotoluene, trimethyl One or more of hexamethylene diamine or dimethyl diamino-dicyclohexyl methane.
Preferably, the viscosity of the base polyurethane prepolymer for use as is 13000~14500mpa.s.
Preferably, the base polyurethane prepolymer for use as is made of the component of following mass percent:
Polyalcohol 20~70%, polyisocyanates 11~25%, catalyst 0.01~0.1%, expands plasticizer 10~20% Chain agent 0.5~1.2%.
Preferably, the polyisocyanates is aliphatic isocyanates, it is further preferable that the polyisocyanates is different Buddhist That ketone diisocyanate, hexamethylene diisocyanate or its tripolymer, dicyclohexyl methyl hydride diisocyanate or 1,4 hexamethylenes One or more of diisocyanate.Using aliphatic isocyanates and polyol reaction, the U.S. seam glue being prepared is not easy Xanthochromia, water-tolerant and intensity with higher.
Preferably, the polyalcohol is in polyoxyethylated polyols, polyoxypropylene polyol or polyester polyol It is one or more of.
Preferably, the mould inhibitor is isothiazolinone biocide mildewcide, one in pyrithione class biocide mildewcide Kind is several, it is highly preferred that the mould inhibitor is 2-methyl-4-isothiazolin-3-one (MIT), the different thiophene of 5- chloro-2-methyl -4- One in oxazoline -3- ketone (CIT), pyrithione sodium salt (SPT) or 2,4,4 '-three chloro- 2 '-hydroxyl-diphenyl ethers Kind is several.
Preferably, the plasticizer is aliphatic diacid esters, phosphoric acid ester, epoxidized soybean oil or epoxyfatty acid formicester One or more of by any proportion composition.
Preferably, the reinforced filling is by talcum powder, kaolin, powdered whiting, precipitated calcium carbonate, active nano carbonic acid One or more of calcium, titanium dioxide, barium sulfate, kaolin or silicon powder are formed by any proportion.
Preferably, the chain extender be dihydric alcohol, it is further preferable that the chain extender be ethylene glycol, 1,2-PD, 1, One or more of 4- butanediol or diethylene glycol (DEG) are formed by any proportion.
Preferably, the catalyst be organic tin, it is further preferable that the catalyst be dibutyl tin dilaurate, One or more of stannous octoate or dibutyl tin acetate are formed by any proportion.
Preferably, the antioxidant is one or more of 245,1010,1035,1076 or 1135 by any proportion group At.
Preferably, the light stabilizer is ultraviolet absorbing agent UV531, ultraviolet absorbing agent UV1130, ultraviolet radiation absorption Agent UV1164, ultraviolet absorbing agent UV1229, ultraviolet absorbing agent UV571, light stabilizer 292, light stabilizer 622 or light are stablized The one or more of agent 770 are formed by any proportion.
Preferably, the deicer is in oxazolidine deicer, p-Methyl benzenesulfonyl isocyanate or triethyl orthoformate One or more by any proportion form.
The present invention protects the preparation method of above-mentioned color inhibition high-strength polyurethane U.S. seam glue simultaneously, and the method is as follows:
S1: plasticizer, reinforced filling, antioxidant, light stabilizer and mould inhibitor are mixed, in 100~110 DEG C of vacuum ring 1.5~2.5h is reacted under border, the moisture content for controlling mixture is less than 300ppm, is then cooled to 40~55 DEG C；
S2: returning nitrogen to normal pressure, and deicer is added and stirs 15~20min, be then added base polyurethane prepolymer for use as, catalyst and Modified molecular screen mixes 0.5~3h under vacuum environment, then returns nitrogen to normal pressure, up to the resistance to Huang after mixture is filtered Become high-strength polyurethane beauty and stitches glue.
In the present invention, the base polyurethane prepolymer for use as the preparation method is as follows:
Polyalcohol and plasticizer are added in vacuum reaction kettle in proportion, are dehydrated under 100 DEG C~110 DEG C of vacuum condition 1.5h~2h, and the moisture content for controlling mixture is less than 300ppm, after being then cooled to 85 DEG C~95 DEG C, in nitrogen protection item Be added under part after polyisocyanates and catalyst carry out reaction 2.5h~4h, 85~95 DEG C at a temperature of, chain extender is added, instead 1~2h is answered, color inhibition high-strength polyurethane performed polymer is obtained.
Compared with prior art, the invention has the following beneficial effects:
The present invention uses aliphatic isocyanates and polyol reaction, and the U.S. seam glue being prepared is not easy xanthochromia, water resistance Intensity good and with higher.Also by by the modified obtained modified molecules of molecular sieve activation powder small molecule aliphatic diamine Sieve is mixed with other components, and a kind of polyurethane U.S. seam glue of one-component has been prepared.U.S. seam glue provided by the invention Curing agent and base polyurethane prepolymer for use as kept apart to the storage stability that ensure that entire component, when use, squeezes out each component, point Son sieve adsorbed moisture solidifies it with base polyurethane prepolymer for use as cross-linking reaction and gives birth to displace small molecule aliphatic diamine curing agent At urea bond, curing rate is fast, rapid reaction and not blistering, the polyurethane U.S. seam glue intensity with higher that is prepared, resistance to Huang Become excellent effect, also there is preferable scratch resistance and stronger mildew-proof function, is particularly suitable for family's use and is particularly suitable for kitchen Defend decoration.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but embodiment the present invention is not done it is any type of It limits.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1
A kind of color inhibition high-strength polyurethane U.S. seam glue, is made of the component of following mass percent:
Wherein, 13X molecular sieve and 1, the mass ratio of 3- cyclohexane diamine are 0.65:0.35, the base polyurethane prepolymer for use as by The component of following mass percent forms:
The preparation method of above-mentioned color inhibition high-strength polyurethane U.S. seam glue, comprising the following steps:
(1), the preparation of base polyurethane prepolymer for use as: polyalcohol and plasticizer are added in vacuum reaction kettle in proportion, at 110 DEG C 2h is dehydrated under vacuum condition, and the moisture content for controlling mixture is less than 300ppm, after being then cooled to 90 DEG C, in nitrogen protection Under the conditions of be added after polyisocyanates and catalyst carry out reaction 5h, 87 DEG C at a temperature of, chain extender is added, reacts 0.5h, Obtain base polyurethane prepolymer for use as, viscosity 14400mpa.s.
(2), the preparation of modified molecular screen: molecular sieve activation powder is placed in Muffle furnace after 300 DEG C of baking 6h slightly cooling and is set Room temperature is cooled in drying tower, modifying agent is shifted after being removed water with 3A molecular sieve and is sealed, is added in modifying agent suitable Molecular sieve activation powder is placed for 24 hours, is taken out the vacuum under room temperature environment and is air-dried surface to get modified molecular screen.
(3), the preparation of color inhibition high-strength polyurethane U.S. seam glue: in proportion by plasticizer, reinforced filling, antioxidant, light Stabilizer, mould inhibitor are added in vacuum reaction kettle, 1.5~2.5h under 100~110 DEG C of vacuum environment, and control mixture Moisture content be less than 300ppm, be then cooled to 40~55 DEG C, then return nitrogen to normal pressure, be added deicer stirring 15~ 20min；Then after color inhibition high-strength polyurethane performed polymer made from step 1 being added to vacuum reaction kettle, formula ratio is added Catalyst and step 2 made from modified molecular screen, 0.5~3h is mixed under vacuum environment, then returns nitrogen to normal pressure, will be mixed After closing object filtering, color inhibition high-strength polyurethane U.S. seam glue is obtained.
Embodiment 2
A kind of color inhibition high intensity polyurethane U.S. seam glue, is made of the component of following mass percent:
Wherein, the mass ratio of 5A molecular sieve and 1,3- cyclohexane diamine is 0.8:0.2, and the base polyurethane prepolymer for use as is by following The component of mass percent forms:
The preparation method of above-mentioned color inhibition high-strength polyurethane U.S. seam glue, comprising the following steps:
(1), the preparation of base polyurethane prepolymer for use as: polyalcohol and plasticizer are added in vacuum reaction kettle in proportion, at 110 DEG C 2h is dehydrated under vacuum condition, and the moisture content for controlling mixture is less than 300ppm, after being then cooled to 90 DEG C, in nitrogen protection Under the conditions of be added after polyisocyanates and catalyst carry out reaction 5h, 87 DEG C at a temperature of, chain extender is added, reacts 0.5h, Obtain base polyurethane prepolymer for use as, viscosity 13600mpa.s.
(2), the preparation of modified molecular screen: molecular sieve activation powder is placed in Muffle furnace after 300 DEG C of baking 6h slightly cooling and is set Room temperature is cooled in drying tower, modifying agent is shifted after being removed water with 3A molecular sieve and is sealed, is added in modifying agent suitable Molecular sieve activation powder is placed for 24 hours, is taken out the vacuum under room temperature environment and is air-dried surface to get modified molecular screen.
(3), the preparation of color inhibition high-strength polyurethane U.S. seam glue: in proportion by plasticizer, reinforced filling, antioxidant, light Stabilizer, mould inhibitor are added in vacuum reaction kettle, 1.5~2.5h under 100~110 DEG C of vacuum environment, and control mixture Moisture content be less than 300ppm, be then cooled to 40~55 DEG C, then return nitrogen to normal pressure, be added deicer stirring 15~ 20min；Then after color inhibition high-strength polyurethane performed polymer made from step 1 being added to vacuum reaction kettle, formula ratio is added Catalyst and step 2 made from modified molecular screen, 0.5~3h is mixed under vacuum environment, then returns nitrogen to normal pressure, will be mixed After closing object filtering, color inhibition high-strength polyurethane U.S. seam glue is obtained.
Embodiment 3
A kind of color inhibition high intensity polyurethane U.S. seam glue, is made of the component of following mass percent:
Wherein, the mass ratio of 13X molecular sieve and trimethylhexane diamine be 0.55:0.45, the base polyurethane prepolymer for use as by with The component of lower mass percent forms:
The preparation method of above-mentioned color inhibition high-strength polyurethane U.S. seam glue, comprising the following steps:
(1), the preparation of base polyurethane prepolymer for use as: polyalcohol and plasticizer are added in vacuum reaction kettle in proportion, at 110 DEG C 2h is dehydrated under vacuum condition, and the moisture content for controlling mixture is less than 300ppm, after being then cooled to 90 DEG C, in nitrogen protection Under the conditions of be added after polyisocyanates and catalyst carry out reaction 5h, 87 DEG C at a temperature of, chain extender is added, reacts 0.5h, Obtain base polyurethane prepolymer for use as, viscosity 13000mpa.s.
(2), the preparation of modified molecular screen: molecular sieve activation powder is placed in Muffle furnace after 300 DEG C of baking 6h slightly cooling and is set Room temperature is cooled in drying tower, modifying agent is shifted after being removed water with 3A molecular sieve and is sealed, is added in modifying agent suitable Molecular sieve activation powder is placed for 24 hours, is taken out the vacuum under room temperature environment and is air-dried surface to get modified molecular screen.
(3), the preparation of color inhibition high-strength polyurethane U.S. seam glue: in proportion by plasticizer, reinforced filling, antioxidant, light Stabilizer, mould inhibitor are added in vacuum reaction kettle, 1.5~2.5h under 100~110 DEG C of vacuum environment, and control mixture Moisture content be less than 300ppm, be then cooled to 40~55 DEG C, then return nitrogen to normal pressure, be added deicer stirring 15~ 20min；Then after color inhibition high-strength polyurethane performed polymer made from step 1 being added to vacuum reaction kettle, formula ratio is added Catalyst and step 2 made from modified molecular screen, 0.5~3h is mixed under vacuum environment, then returns nitrogen to normal pressure, will be mixed After closing object filtering, color inhibition high-strength polyurethane U.S. seam glue is obtained.
Embodiment 4
The formula and preparation method of color inhibition high intensity polyurethane U.S. seam glue provided in this embodiment are referring to embodiment 1, no It is with place, 13X molecular sieve and 1 in the present embodiment 1, the mass ratio of 3- cyclohexane diamine is 0.90:0.10.
Comparative example 1
The formula and preparation method reference embodiment 1 for the polyurethane U.S. seam glue that this comparative example provides, the difference is that, this Comparative example omits the step in preparation method without modified molecular screen, that is, 13X molecular sieve (absorption 1,3- cyclohexane diamine) (2)。
Comparative example 2
The formula and preparation method reference embodiment 1 for the polyurethane U.S. seam glue that this comparative example provides, the difference is that, this Base polyurethane prepolymer for use as in comparative example is made of the component of following mass percent:
Thus being formulated base polyurethane prepolymer for use as viscosity obtained is 16700mpa.s.
Comparative example 3
The formula and preparation method reference embodiment 1 for the polyurethane U.S. seam glue that this comparative example provides, the difference is that, this The molecular sieve activation powder that modified molecular screen is selected in comparative example is that 3A activates powder.
Comparative example 4
The formula and preparation method reference embodiment 1 for the polyurethane U.S. seam glue that this comparative example provides, the difference is that, this The curing agent that modified molecular screen is selected in comparative example is ethylenediamine.
The performance test results for the polyurethane U.S. seam glue that 1 Examples 1 to 4 of table and comparative example 1~4 provide
Note: mildew resistance is tested referring to GB/T1741, and anti-yellowing property is tested referring to HG/T4363-2012, is drawn It stretches intensity to be tested referring to GB/T528, all test pieces are tested after conserving 168h under 23 DEG C, 50% humidity environment.
As a result as can be seen that Examples 1 to 4 Sino-U.S. seam glue intensity is high, anti-yellowing property is good, in embodiment 4 molecular sieve with The mass ratio of curing agent is excessive, causes curing dose in joint trimming agent inadequate, and curing rate is slightly slow, and intensity is also slightly lower, and has light Microbubble, interfacial failure is more, but still meets requirement；Modified molecular sieve, surface drying is added due to not having in comparative example 1 Time and curing rate are all slower than each embodiment, and bubble is serious after solidification, and intensity is also lower than each embodiment, to ceramic tile Caking property shows as interfacial failure.Three-functionality-degree polyethers amount increases in comparative example 2, and two degree of functionality polyethers amounts are reduced, and the degree of cross linking increases Greatly, viscosity is caused to become larger, intensity is lower, bonding with ceramic tile to be also deteriorated.The 3A of comparative example 3 activates powder and absorbs curing agent, due to The aperture of 3A is smaller, can not absorb curing agent, so having many bubbles after solidification.Comparative example 4 due to ethylenediamine molecular weight compared with It is low, and be dissolved in water, cause it is more difficult displace ethylenediamine curing agent with water, curing rate is slack-off, and intensity also reduces, viscous with ceramic tile Knot is deteriorated.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than limiting the scope of the invention, although The present invention is explained in detail referring to embodiment, those skilled in the art should understand that, it can be to of the invention Technical solution is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention.

Claims (10)

1. a kind of color inhibition high-strength polyurethane beauty stitches glue, which is characterized in that the beauty stitches glue by the group of following mass percent Part composition:
Base polyurethane prepolymer for use as 20~60%, plasticizer 0~10%, reinforced filling 30~60%, modified molecular screen 2~5%, catalysis Agent 0.02~1%, antioxidant 0.1~1%, light stabilizer 0.1~1%, mould inhibitor 0.5~3%, deicer 0.5~1%；Institute The viscosity for stating base polyurethane prepolymer for use as is 10000~15000mp.s；
Wherein, the modified molecular screen is made of the component of following mass percent:
Molecular sieve activation powder 40~80%, curing agent 20~60%；The molecular sieve is that 5A activated molecular sieve and/or 13X are activated Molecular sieve, the curing agent are small molecule aliphatic diamine, and the molecular weight of the small molecule aliphatic diamine is 80~250.
2. color inhibition high-strength polyurethane beauty stitches glue according to claim 1, which is characterized in that in the modified molecular screen, The mass ratio of molecular sieve activation powder and curing agent is 0.4~0.8:0.2~0.6.
3. color inhibition high-strength polyurethane beauty stitches glue according to claim 2, which is characterized in that in the modified molecular screen, The mass ratio of molecular sieve activation powder and curing agent is 0.55~0.75:0.25~0.45.
4. color inhibition high-strength polyurethane beauty stitches glue according to claim 1, which is characterized in that the system of the modified molecular screen Preparation Method is as follows:
By the dry water removal of molecular sieve activation dried bean noodles, placement for 24 hours or more is then mixed with curing agent, air-dries molecular sieve surface finally to remove The curing agent for going to surface to adhere to is to get the modified molecular screen.
5. color inhibition high-strength polyurethane beauty stitches glue according to claim 1, which is characterized in that the small molecule aliphatic two Amine is 1,3- cyclohexane diamine, 1,3- diamine hexahydrotoluene, trimethylhexane diamine or dimethyl diamino-dicyclohexyl methane One or more of.
6. color inhibition high-strength polyurethane beauty stitches glue according to claim 1, which is characterized in that the base polyurethane prepolymer for use as Viscosity is 13000~14500mpa.s.
7. according to claim 1 color inhibition high-strength polyurethane beauty stitch glue, which is characterized in that the base polyurethane prepolymer for use as by The component composition of following mass percent:
Polyalcohol 20~70%, plasticizer 10~20%, polyisocyanates 11~25%, catalyst 0.01~0.1%, chain extender 0.5~1.2%.
8. color inhibition high-strength polyurethane beauty stitches glue according to claim 7, which is characterized in that the polyisocyanates is rouge Fat race isocyanates.
9. color inhibition high-strength polyurethane beauty stitches glue according to claim 7, which is characterized in that the polyalcohol is polyoxygenated One or more of ethylene polyalcohol, polyoxypropylene polyol or polyester polyol.
10. the preparation method of any color inhibition high-strength polyurethane U.S. seam glue of claim 1~9, which is characterized in that described Method is as follows:
S1: plasticizer, reinforced filling, antioxidant, light stabilizer and mould inhibitor are mixed, under 100~110 DEG C of vacuum environment 1.5~2.5h is reacted, the moisture content for controlling mixture is less than 300ppm, is then cooled to 40~55 DEG C；
S2: nitrogen is returned to normal pressure, deicer is added and stirs 15~20min, base polyurethane prepolymer for use as, catalyst and modification is then added Molecular sieve mixes 0.5~3h under vacuum environment, then returns nitrogen to normal pressure, up to the color inhibition height after mixture is filtered Intensity polyurethane beauty stitches glue.
CN201910452931.8A 2019-05-28 2019-05-28 A kind of color inhibition high-strength polyurethane U.S. seam glue and preparation method thereof Pending CN110093138A (en)

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Application publication date: 20190806