CN110041489A - A kind of polyurethane sealant resistance to migration plasticizer and a kind of polyurethane building sealant - Google Patents
A kind of polyurethane sealant resistance to migration plasticizer and a kind of polyurethane building sealant Download PDFInfo
- Publication number
- CN110041489A CN110041489A CN201910324832.1A CN201910324832A CN110041489A CN 110041489 A CN110041489 A CN 110041489A CN 201910324832 A CN201910324832 A CN 201910324832A CN 110041489 A CN110041489 A CN 110041489A
- Authority
- CN
- China
- Prior art keywords
- resistance
- migration
- plasticizer
- sealant
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
Abstract
The present invention provides one kind resistance to migration plasticizer by including that the component of following mass percent is prepared: polyoxypropylene polyol 70~92%；Polyisocyanates 5~18%；End-capping reagent 1~15%；Wherein, viscosity of resistance to migration plasticizer under the conditions of 25 DEG C is 10000~35000mpas.Plasticizer resistance to migration provided by the invention can be good, can meet requirement of the European Union outlet to polyurethane building sealant product by RoHS and REACH requirement as the environmental-protecting performance for the polyurethane sealant that plasticizer is prepared.
Description
Technical field
The present invention relates to sealant technical fields, more particularly, to a kind of polyurethane sealant plasticizer of resistance to migration
And a kind of polyurethane building sealant.
Background technique
Polyurethane sealant is widely used in building field, has flexibility good, and adhering and sealing is functional, chemical-resistance
Excellent feature.General polyurethane sealant is to enhance its flexibility, needs to be added plasticizer and is plasticized, and assigns sealant more
Good elastic effect.
Currently used plasticizer neighbour benzene class plasticizing efficiency highest, mainly there is butyl phthalate, phthalic acid fourth
Benzyl ester, octyl phthalate, phthalic acid nonyl ester and phthalic acid last of the ten Heavenly stems ester etc..On December 12nd, 2014, Europe chemistry
Product management board (ECHA) announces that phthalic acid that monooctyl ester (DEHP) becomes same concern substance because its is endocrine disrupting, this
Sample has been that the dioctyl phthalate of high concern substance (SVHC) increases same concern substance again outside genotoxicity originally
Harm.For the limitation requirement for coping with European Union, the general sealant for exporting European Union generally uses phthalic acid nonyl ester and adjacent benzene
The temporary non-regulated substance such as dioctyl phthalate last of the ten Heavenly stems ester is as plasticizer.Phthalic acid nonyl ester and phthalic acid last of the ten Heavenly stems ester phase in sealant
Larger to molecular weight, wherein phthalic acid last of the ten Heavenly stems ester molecule amount maximum also only has 446.74, equally will appear in use and slightly moves
The case where shifting.Currently, the sealant of outlet European Union many times necessarily requires to authenticate by RoHS and REACH, general sealant
Be unable to satisfy requirement be primarily due to it is exceeded containing DEHP or Theil indices and solvent.
Therefore, it is necessary to which to research and develop a kind of environmentally friendly, resistance to migration plasticizer and polyurethane suitable for polyurethane sealant close
Sealing.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of resistance to migrations of polyurethane sealant to be plasticized
Agent, plasticizer resistance to migration provided by the invention can be good, as the environmental protection for the polyurethane sealant that plasticizer is prepared
Performance can meet requirement of the European Union outlet to polyurethane building sealant product by RoHS and REACH requirement.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of polyurethane sealant plasticizer of resistance to migration, the resistance to migration plasticizer is by including following mass percent
Component be prepared:
Polyoxypropylene polyol 70~92%；
Polyisocyanates 5~18%；
End-capping reagent 1~15%；
Wherein, viscosity of resistance to migration plasticizer under the conditions of 25 DEG C is 10000~35000mpas.
Preferably, the end-capping reagent is single functionality small molecular alcohol.
Preferably, the end-capping reagent is one or more of ethyl alcohol, butanol or n-octyl alcohol.
Preferably, viscosity of resistance to migration plasticizer under the conditions of 25 DEG C is 10000~25000mpas.
The present invention protects the preparation method of above-mentioned resistance to migration plasticizer simultaneously, and described method includes following steps:
S1: polyoxypropylene polyol is sufficiently mixed, be rapidly heated to 100~120 DEG C of 2~4h of dehydrated under vacuum to its
Moisture is less than 200ppm, is then cooled to 50~70 DEG C；
S2: being added polyisocyanates, is reacted to theoretical end point by titration NCO content determination under the conditions of 70~105 DEG C,
Then end-capping reagent is added, by infrared NCO characteristic absorption peak disappear determine reaction end, be warming up to 100~120 DEG C of vacuum take off it is small
1~2.5h of molecule, obtains the plasticizer of resistance to migration.
The present invention protects a kind of polyurethane building sealant simultaneously, and the sealant includes the group of following mass percent
Point:
Polyurethane building sealant provided by the invention blocks tree using the polyoxypropylene polyol of above-mentioned macromolecule
Non-neighboring benzene class plasticizer of the rouge as sealant system, product have the characteristics that the migration of plasticizer difficulty, the polyurethane sealant
The polyurethane sealant that environmental-protecting performance is required by RoHS and REACH meets European Union outlet to polyurethane building sealant product
Requirement.
In addition, the present invention substitutes organotin catalysts using organo-bismuth class environmental protection catalyst, product is not stanniferous, and tin is not present
Content limitation；After adding silane adhesion promotor, sealant is functional with substrate bonding；Add moisture scavenger, water removal effect
Fruit is good, and the sealant shelf-life is longer；The entire formula and technical process of polyurethane building sealant provided by the invention are not added
Any hazardous solvent；One-component formulation, it is easy for construction without mixing when use.
Preferably, the base polyurethane prepolymer for use as includes that the component of following mass percent is prepared:
Polyoxypropylene polyol 70~95%；
Polyisocyanates 5~30%.
Further, the base polyurethane prepolymer for use as is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 100~120 DEG C of 2~4h of dehydrated under vacuum to its moisture, be then cooled to 50
~70 DEG C；
(4) polyisocyanates of formula equivalent is added, is reacted in 70~105 DEG C of conditions by titration NCO content determination
After theoretical end point, base polyurethane prepolymer for use as is obtained.
Further, the base polyurethane prepolymer for use as isocyanate content be 0.2~5%, 25 DEG C of viscosity be 12000~
35000mpa·s。
Preferably, the polyoxypropylene polyol is polyoxyethylene glycol and/or polypropylene oxide trihydroxylic alcohol.Its
In, Polyoxypropylene diol molecular weight is 2000~8000, and polypropylene oxide trihydroxylic alcohol molecular weight is 3000~6000.
Preferably, the polyisocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, oneself is two different by 1,6-
One or more of cyanate or isophorone diisocyanate.
Preferably, the filler be PVC paste resin, precipitated calcium carbonate, powdered whiting, nanometer calcium carbonate, talcum powder or
One or more of calcined kaolin.
Preferably, the thixotropic agent is one of hydrophobic gas-phase silica, carbon black, rilanit special or polyamide or several
Kind.
Preferably, the silane adhesion promotor is the silane without active H, and further, the silane adhesion promotes
Agent is γ-glycidoxypropyltrietandysilane andysilane, γ-ureidopropyltriethoxysilane, γ-ureido-propyl trimethoxy
One in base silane, γ-methacryloxypropyl trimethoxy silane or γ-methacrylamido isopropoxy silane
Kind is several.
Preferably, the catalyst be organic bismuth catalyst, further, the catalyst be capric acid bismuth, lauric acid bismuth,
Isooctyl acid bismuth, one or more of bismuth naphthenate or bismuth carboxylate.
Preferably, the moisture scavenger is trimethyl orthoformate, to sulfonyloxy methyl isocyanates or oxazole alkanes moisture
One or more of scavenger.
The present invention also provides the preparation methods of above-mentioned polyurethane sealant, and described method includes following steps:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) will base polyurethane prepolymer for use as be added mixer in, under the conditions of 0.09 ± 0.005MPa of vacuum stir 10~
20min, temperature are controlled at 25~45 DEG C；
(3) after again mixing resistance to migration plasticizer with base polyurethane prepolymer for use as, 20~40min is stirred；
(4) filler and moisture scavenger after drying is added stir under the conditions of 50~70 DEG C of nitrogen atmospheres after mixing
Mix 30~50min；
(5) silane adhesion promotor and environmental protection catalyst are added under the conditions of nitrogen protection, under the conditions of 50~70 DEG C after
It is continuous that 1~1.5h is mixed；
(6) material goes out kettle, detection, subpackage dress, obtains resistance to migration environment-protecting polyurethane sealant.
Compared with prior art, the invention has the following beneficial effects:
1. the polyoxypropylene polyol end block resins using macromolecule are plasticized as the non-neighboring benzene class of sealant system
Agent, product have the characteristics that the migration of plasticizer difficulty；2. substituting organotin catalysts using organo-bismuth class environmental protection catalyst, product is not
Stanniferous, there is no Theil indices to limit；3. sealant is functional with substrate bonding after adding silane adhesion promotor；4. adding
Moisture scavenger, water removal effect is good, and the sealant shelf-life is longer；5. it is molten that any nocuousness is not added for entire formula and technical process
Agent；6. one-component formulation, easy for construction without mixing when use；7. the resistance to migration environment-protecting polyurethane of one pack system of the invention is built
The preparation method of sealant is built, there is simple process, is convenient for industrialized feature.
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 polyurethane sealant plasticizer of resistance to migration, the resistance to migration plasticizer is by including following mass percent
Component is prepared:
Polyoxypropylene diol (4000) 90.1%
Toluene di-isocyanate(TDI) 7.8%
Ethyl alcohol 2.1%
Above-mentioned resistance to migration plasticizer is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 115 DEG C of dehydrated under vacuum 2.5h to its moisture, be then cooled to 55 DEG C；
(4) polyisocyanates of addition formula equivalent is determined by titration NCO content in 80 DEG C of conditions and is reacted to theory eventually
After point.
(5) end-capping reagent of formula equivalent is added, is disappeared by infrared NCO characteristic absorption peak and determines that reaction is reached home, risen
Temperature to 100 DEG C of vacuum take off small molecule 1h, obtain the plasticizer of resistance to migration.
Above-mentioned resistance to 25 DEG C of viscosity of migration plasticizer are 12500mpas.
Embodiment 2
A kind of polyurethane sealant plasticizer of resistance to migration, the resistance to migration plasticizer is by including following mass percent
Component is prepared:
Polyoxypropylene diol (3000) 85.8%
Toluene di-isocyanate(TDI) 10%
Butanol 4.2%
Above-mentioned resistance to migration plasticizer is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 110 DEG C of dehydrated under vacuum 3h to its moisture, be then cooled to 55 DEG C；
(4) polyisocyanates of addition formula equivalent is determined by titration NCO content in 85 DEG C of conditions and is reacted to theory eventually
After point.
(5) end-capping reagent of formula equivalent is added, is disappeared by infrared NCO characteristic absorption peak and determines that reaction is reached home, risen
Temperature to 100 DEG C of vacuum take off small molecule 1.5h, obtain the plasticizer of resistance to migration.
Above-mentioned resistance to 25 DEG C of viscosity of migration plasticizer are 9600mpas.
Embodiment 3
A kind of polyurethane sealant plasticizer of resistance to migration, the resistance to migration plasticizer is by including following mass percent
Component is prepared:
Polyoxypropylene diol (2000) 73.9%
Isophorone diisocyanate 16.5%
N-octyl alcohol 9.6%
Above-mentioned resistance to migration plasticizer is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 120 DEG C of dehydrated under vacuum 2.5h to its moisture, be then cooled to 70 DEG C；
(4) polyisocyanates of formula equivalent is added, theory is reacted to by titration NCO content determination in 100 DEG C of conditions
After terminal.
(5) end-capping reagent of formula equivalent is added, is disappeared by infrared NCO characteristic absorption peak and determines that reaction is reached home, risen
Temperature to 118 DEG C of vacuum take off small molecule 1.5h, obtain the plasticizer of resistance to migration.
Above-mentioned resistance to 25 DEG C of viscosity of migration plasticizer are 7800mpas.
Embodiment 4
A kind of polyurethane sealant plasticizer of resistance to migration, the resistance to migration plasticizer is by including following mass percent
Component is prepared:
Above-mentioned resistance to migration plasticizer is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 115 DEG C of dehydrated under vacuum 3.5h to its moisture, be then cooled to 68 DEG C；
(4) polyisocyanates of formula equivalent is added, theory is reacted to by titration NCO content determination in 102 DEG C of conditions
After terminal.
(5) end-capping reagent of formula equivalent is added, is disappeared by infrared NCO characteristic absorption peak and determines that reaction is reached home, risen
Temperature to 115 DEG C of vacuum take off small molecule 1.5h, obtain the plasticizer of resistance to migration.
Above-mentioned resistance to 25 DEG C of viscosity of migration plasticizer are 22500mpas.
Application examples 1
A kind of resistance to migration environment-protecting polyurethane building sealant of one pack system, the raw material including following mass percentage composition:
Wherein, above-mentioned base polyurethane prepolymer for use as is the raw material by being prepared, including following mass percentage composition:
Polyoxypropylene diol (2000) 28.2%
Polypropylene oxide trihydroxylic alcohol (5000) 56.3%
Methyl diphenylene diisocyanate 15.5%
Above-mentioned base polyurethane prepolymer for use as is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 115 DEG C of dehydrated under vacuum 2.5h to its moisture, be then cooled to 50 DEG C；
(4) polyisocyanates of addition formula equivalent is determined by titration NCO content in 80 DEG C of conditions and is reacted to theory eventually
After point, base polyurethane prepolymer for use as is obtained.
Above-mentioned base polyurethane prepolymer for use as isocyanate content is 2.6%, and 25 DEG C of viscosity are 28000mpas.
The preparation method of the above-mentioned resistance to migration environment-protecting polyurethane building sealant of one pack system, comprising the following specific steps
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) base polyurethane prepolymer for use as is added in mixer, stirs 15min under the conditions of 0.09 ± 0.005MPa of vacuum, temperature
Degree control is at 40 DEG C；
(3) after again mixing resistance to migration plasticizer with base polyurethane prepolymer for use as, 35min is stirred；
(4) filler and moisture scavenger after drying is added stir under the conditions of 55 DEG C of nitrogen atmospheres after mixing
50min；
(5) adhesion promoters and environmental protection catalyst are added under the conditions of nitrogen protection, continuess to mix and stirs under the conditions of 55 DEG C
Mix 1h；
(6) material goes out kettle, detection, subpackage dress, obtains resistance to migration environment-protecting polyurethane building sealant.
Application examples 2
A kind of resistance to migration environment-protecting polyurethane building sealant of one pack system, the raw material including following mass percentage composition:
Wherein, above-mentioned base polyurethane prepolymer for use as is the raw material by being prepared, including following mass percentage composition:
Polyoxypropylene diol (4000) 36.4%
Polypropylene oxide trihydroxylic alcohol (5000) 54.6%
Toluene di-isocyanate(TDI) 9.0%
Above-mentioned base polyurethane prepolymer for use as is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 110 DEG C of dehydrated under vacuum 3h to its moisture, be then cooled to 55 DEG C；
(4) polyisocyanates of addition formula equivalent is determined by titration NCO content in 85 DEG C of conditions and is reacted to theory eventually
After point, base polyurethane prepolymer for use as is obtained.
Above-mentioned base polyurethane prepolymer for use as isocyanate content is 2.1%, and 25 DEG C of viscosity are 32000mpas.
The preparation method of the above-mentioned resistance to migration environment-protecting polyurethane building sealant of one pack system, comprising the following specific steps
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) base polyurethane prepolymer for use as is added in mixer, stirs 20min under the conditions of 0.09 ± 0.005MPa of vacuum, temperature
Degree control is at 45 DEG C；
(3) after again mixing resistance to migration plasticizer with base polyurethane prepolymer for use as, 25min is stirred；
(4) filler and moisture scavenger after drying is added stir under the conditions of 55 DEG C of nitrogen atmospheres after mixing
50min；
(5) adhesion promoters and environmental protection catalyst are added under the conditions of nitrogen protection, continuess to mix and stirs under the conditions of 60 DEG C
Mix 1h；
(6) material goes out kettle, detection, subpackage dress, obtains resistance to migration environment-protecting polyurethane building sealant.
Application examples 3
A kind of resistance to migration environment-protecting polyurethane building sealant of one pack system, the raw material including following mass percentage composition:
Wherein, above-mentioned base polyurethane prepolymer for use as is the raw material by being prepared, including following mass percentage composition:
Polyoxypropylene diol (4000) 30.7%
Polypropylene oxide trihydroxylic alcohol (6000) 61.3%
Toluene di-isocyanate(TDI) 8.0%
Above-mentioned base polyurethane prepolymer for use as is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 110 DEG C of dehydrated under vacuum 3.5h to its moisture, be then cooled to 55 DEG C；
(4) polyisocyanates of addition formula equivalent is determined by titration NCO content in 85 DEG C of conditions and is reacted to theory eventually
After point, base polyurethane prepolymer for use as is obtained.
Above-mentioned base polyurethane prepolymer for use as isocyanate content is 1.9%, and 25 DEG C of viscosity are 27000mpas.
The preparation method of the above-mentioned resistance to migration environment-protecting polyurethane building sealant of one pack system, comprising the following specific steps
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) will base polyurethane prepolymer for use as be added mixer in, under the conditions of 0.09 ± 0.005MPa of vacuum stir 10~
20min, temperature are controlled at 25~45 DEG C；
(3) after again mixing resistance to migration plasticizer with base polyurethane prepolymer for use as, 20~40min is stirred；
(4) filler and moisture scavenger after drying is added stir under the conditions of 50~70 DEG C of nitrogen atmospheres after mixing
Mix 30~50min；
(5) silane adhesion promotor and environmental protection catalyst are added under the conditions of nitrogen protection, under the conditions of 50~70 DEG C after
It is continuous that 1~1.5h is mixed；
(6) material goes out kettle, detection, subpackage dress, obtains resistance to migration environment-protecting polyurethane sealant.
Application examples 4
A kind of resistance to migration environment-protecting polyurethane building sealant of one pack system, the raw material including following mass percentage composition:
Wherein, above-mentioned base polyurethane prepolymer for use as is the raw material by being prepared, including following mass percentage composition:
Polyoxypropylene diol (2000) 21.9%
Polypropylene oxide trihydroxylic alcohol (6000) 65.8%
Isophorone diisocyanate 12.3%
Above-mentioned base polyurethane prepolymer for use as is prepared by following methods:
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) polyoxypropylene polyol is added in the reaction kettle equipped with blender, nitrogen inlet and thermometer sufficiently mixed
It closes；
(3) it is rapidly heated and is less than 200ppm to 115 DEG C of dehydrated under vacuum 3h to its moisture, be then cooled to 65 DEG C；
(4) polyisocyanates of formula equivalent is added, theory is reacted to by titration NCO content determination in 100 DEG C of conditions
After terminal, base polyurethane prepolymer for use as is obtained.
Above-mentioned base polyurethane prepolymer for use as isocyanate content is 2.3%, and 25 DEG C of viscosity are 23000mpas.
Above-mentioned resistance to migration environment-protecting polyurethane building sealant of one pack system and preparation method thereof, comprising the following specific steps
(1) component for pressing above-mentioned quality proportioning, prepares raw material；
(2) base polyurethane prepolymer for use as is added in mixer, stirs 18min under the conditions of 0.09 ± 0.005MPa of vacuum, temperature
Degree control is at 43 DEG C；
(3) after again mixing resistance to migration plasticizer with base polyurethane prepolymer for use as, 30min is stirred；
(4) filler and moisture scavenger after drying is added stir under the conditions of 65 DEG C of nitrogen atmospheres after mixing
45min；
(5) adhesion promoters and environmental protection catalyst are added under the conditions of nitrogen protection, continuess to mix and stirs under the conditions of 65 DEG C
Mix 1h；
(6) material goes out kettle, detection, subpackage dress, obtains resistance to migration environment-protecting polyurethane building sealant.
Comparative example 1
The resistance to migration environment-protecting polyurethane building sealant of one pack system that this comparative example provides is except selection phthalic acid last of the ten Heavenly stems ester
Except the plasticizer of resistance to migration in alternate application example 1, other formulas and method are identical as application examples 1.
Comparative example 2
Resistance to migration plasticizer passes through packet in the resistance to migration environment-protecting polyurethane building sealant of one pack system that this comparative example provides
The component for including following mass percent is prepared:
Polyoxypropylene diol (4000) 69.5%；
Toluene di-isocyanate(TDI) 21.9%；
Ethyl alcohol 8.6%；
Above-mentioned resistance to 25 DEG C of viscosity of migration plasticizer are 9500mpas.
The preparation method is the same as that of Example 1 for above-mentioned resistance to migration plasticizer, in this comparative example it is other formula and preparation method with
Application examples 1 is identical.
The performance for the polyurethane building sealant that above-mentioned each application examples and comparative example are prepared is tested, test side
Method is as follows, and test result see the table below 1.
(1) surface drying time is tested by GB/T13477.
(2) tensile strength and elongation at break are tested by GB/T 528.
(3) resistance to migration is tested
Using vinyl-vinyl acetate copolymer as absorbing sheet, specimen size 50mm*50mm*1mm, absorbing sheet having a size of
60mm*60mm*2mm, pressure are 5kg counterweight weight, and temperature is 70 DEG C, and the time is for 24 hours, to test quality of the plasticizer in absorbing sheet
Bodies lost weight.RoHS and REACH certification is tested using sealant inspection SGS.
The performance for the polyurethane building sealant that the above-mentioned each application examples of table 1 and comparative example are prepared
By the performance test data of table 1 it is found that in Examples 1 to 4 resistance to migration environment-friendly type build polyurethane build sealant environmental protection
It is functional, it can be transferred through RoHS certification and REACH certification, be able to satisfy European Union's export requirement.O-phthalic is used in comparative example 1
Although sour last of the ten Heavenly stems ester and organic bismuth catalyst can also be authenticated by RoHS and REACH is authenticated, meet European Union's export requirement, adjacent benzene two
Formic acid last of the ten Heavenly stems ester resistance to migration is apparently higher than Examples 1 to 4, and environment-friendly type is relatively poor.Although the plasticizer that comparative example 2 uses also can
By RoHS certification and REACH certification, meet European Union's export requirement, but since free isocyanate is excessively high, small molecule after sealing end
More, resistance to migration is also bad.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected
The limitation for protecting range, although the specific embodiment part is described in detail the present invention, the ordinary skill people of this field
Member is it should be appreciated that can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from inventive technique scheme
Spirit and scope.
Claims (10)
1. a kind of polyurethane sealant plasticizer of resistance to migration, which is characterized in that the resistance to migration plasticizer is by including as follows
The component of mass percent is prepared:
Polyoxypropylene polyol 70~92%；
Polyisocyanates 5~18%；
End-capping reagent 1~15%；
Wherein, viscosity of resistance to migration plasticizer under the conditions of 25 DEG C is 10000~35000mpas.
2. the plasticizer of resistance to migration according to claim 1, which is characterized in that the end-capping reagent is single functionality small molecular alcohol.
3. the plasticizer of resistance to migration according to claim 2, which is characterized in that the end-capping reagent is ethyl alcohol, butanol or n-octyl alcohol
One or more of.
4. the plasticizer of resistance to migration according to claim 1, which is characterized in that the resistance to migration plasticizer is 25 DEG C under the conditions of
Viscosity is 10000~25000mpas.
5. the preparation method of resistance to migration plasticizer described in Claims 1 to 4, which comprises the steps of:
S1: polyoxypropylene polyol is sufficiently mixed, and is rapidly heated to 100~120 DEG C of 2~4h of dehydrated under vacuum to its moisture
Less than 200ppm, it is then cooled to 50~70 DEG C；
S2: being added polyisocyanates, is reacted to theoretical end point by titration NCO content determination under the conditions of 70~105 DEG C, then
End-capping reagent is added, is disappeared by infrared NCO characteristic absorption peak and determines reaction end, is warming up to 100~120 DEG C of vacuum and takes off small molecule
1~2.5h obtains the plasticizer of resistance to migration.
6. a kind of polyurethane building sealant, which is characterized in that the sealant includes the component of following mass percent:
Wherein, the resistance to migration plasticizer is any plasticizer of resistance to migration of Claims 1 to 4.
7. polyurethane building sealant according to claim 6, which is characterized in that the base polyurethane prepolymer for use as includes following matter
The component of amount percentage is prepared:
Polyoxypropylene polyol 70~95%；
Polyisocyanates 5~30%.
8. polyurethane building sealant according to claim 6, which is characterized in that the base polyurethane prepolymer for use as isocyanates contains
It is 12000~35000mpas that amount, which is 0.2~5%, 25 DEG C of viscosity,.
9. polyurethane building sealant according to claim 6, which is characterized in that the polyoxypropylene polyol is polyoxy
Change ethylene dihydric alcohol and/or polypropylene oxide trihydroxylic alcohol.
10. polyurethane building sealant according to claim 6, which is characterized in that the polyisocyanates is that toluene two is different
One of cyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate are several
Kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910324832.1A CN110041489A (en) | 2019-04-22 | 2019-04-22 | A kind of polyurethane sealant resistance to migration plasticizer and a kind of polyurethane building sealant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910324832.1A CN110041489A (en) | 2019-04-22 | 2019-04-22 | A kind of polyurethane sealant resistance to migration plasticizer and a kind of polyurethane building sealant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110041489A true CN110041489A (en) | 2019-07-23 |
Family
ID=67278384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910324832.1A Pending CN110041489A (en) | 2019-04-22 | 2019-04-22 | A kind of polyurethane sealant resistance to migration plasticizer and a kind of polyurethane building sealant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110041489A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525654A (en) * | 1990-09-18 | 1996-06-11 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethane-based sealing and adhesive compositions containing special diurethane plasticizers |
| US6218462B1 (en) * | 1999-12-03 | 2001-04-17 | Bayer Corporation | Liquid ultra-high molecular weight polyurethane plasticizers |
| US20020132915A1 (en) * | 2000-12-20 | 2002-09-19 | Pantone Richard S. | Liquid polyurethane plasticizers containing allophanate and/or carbodiimide and/or uretonimine groups |
| CN101805588A (en) * | 2010-03-05 | 2010-08-18 | 中科院广州化灌工程有限公司 | Polyurethane road caulking sealant with good durability and production process |
| JP2010215829A (en) * | 2009-03-18 | 2010-09-30 | Sanyo Chem Ind Ltd | Curable polyurethane composition |
| CN101906283A (en) * | 2010-08-31 | 2010-12-08 | 东莞市普赛达密封粘胶有限公司 | Internal plasticization type mono-component polyurethane seal gum |
| CN102504750A (en) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | Polyurethane sealant with good initial adhesion |
| CN105086423A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Low-hardness casted polyurethane elastomer with plasticizer and preparation method for polyurethane elastomer |
| CN105733491A (en) * | 2016-04-18 | 2016-07-06 | 广东普赛达密封粘胶有限公司 | Low-TVOC polyurethane weather-proof sealant and preparation method thereof |
-
2019
- 2019-04-22 CN CN201910324832.1A patent/CN110041489A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525654A (en) * | 1990-09-18 | 1996-06-11 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethane-based sealing and adhesive compositions containing special diurethane plasticizers |
| US6218462B1 (en) * | 1999-12-03 | 2001-04-17 | Bayer Corporation | Liquid ultra-high molecular weight polyurethane plasticizers |
| US20020132915A1 (en) * | 2000-12-20 | 2002-09-19 | Pantone Richard S. | Liquid polyurethane plasticizers containing allophanate and/or carbodiimide and/or uretonimine groups |
| JP2010215829A (en) * | 2009-03-18 | 2010-09-30 | Sanyo Chem Ind Ltd | Curable polyurethane composition |
| CN101805588A (en) * | 2010-03-05 | 2010-08-18 | 中科院广州化灌工程有限公司 | Polyurethane road caulking sealant with good durability and production process |
| CN101906283A (en) * | 2010-08-31 | 2010-12-08 | 东莞市普赛达密封粘胶有限公司 | Internal plasticization type mono-component polyurethane seal gum |
| CN102504750A (en) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | Polyurethane sealant with good initial adhesion |
| CN105086423A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Low-hardness casted polyurethane elastomer with plasticizer and preparation method for polyurethane elastomer |
| CN105733491A (en) * | 2016-04-18 | 2016-07-06 | 广东普赛达密封粘胶有限公司 | Low-TVOC polyurethane weather-proof sealant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 强涛涛 编著: "《合成革化学品》", 31 July 2016, 中国轻工业出版社 * |
| 杨淑丽 伊廷会 等编: "《密封胶粘剂》", 30 April 2004, 中国石化出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2420554C2 (en) | Single-component anhydrous coating composition for sealing building structures and flat roofs | |
| CN104559734A (en) | Double-component chemical-reaction thixotropic polyurethane waterproof paint and preparation method thereof | |
| CN101838513B (en) | Preparation method of bi-component siloxane modified polyurethane sealant | |
| EP1799738A1 (en) | Low volatile isocyanate monomer containing polyurethane prepolymer and adhesive system | |
| EP2721117B1 (en) | Hybrid sealant composition | |
| CN109777338A (en) | High-intensitive high elongation at tear monocomponent polyurethane adhesive and preparation method | |
| CN108949090B (en) | Solvent-free two-component polyurethane sealant and preparation method thereof | |
| CN111117465B (en) | Environment-friendly single-component polyurethane waterproof coating | |
| CN112708340A (en) | Anti-sagging single-component polyurethane waterproof coating capable of being sprayed and constructed | |
| CN114269803A (en) | One-component polyurethane prepolymer composition | |
| CN109207111A (en) | A kind of one-component polyurethane sealant and preparation method thereof | |
| CN107033827A (en) | A kind of single component silane modified polyether seal glue for building and preparation method thereof | |
| CN109535366A (en) | A kind of secondary amino silanes modified polyether polymer and preparation method thereof | |
| CN105504787A (en) | Silane-capped polyurethane composition and preparation method and application thereof | |
| CN114031767A (en) | Cyclic carbonate prepolymer, silane modified non-isocyanate polyurethane resin, and preparation methods and applications thereof | |
| CN113444441A (en) | Modified single-component polyurethane waterproof coating composition, modified single-component polyurethane waterproof coating, and preparation method and application thereof | |
| WO2013164413A1 (en) | Two-component hot-melt adhesive | |
| CN111117549B (en) | Single-component polyurethane sealant prepared by using PAPI (polymethylacrylate polyimide) | |
| CN110041489A (en) | A kind of polyurethane sealant resistance to migration plasticizer and a kind of polyurethane building sealant | |
| JP2007169432A (en) | Solventless polyurethane composition and its cured product | |
| CN111234764B (en) | Polyurethane corner-combining adhesive with high bonding strength and preparation method thereof | |
| CN108753241A (en) | Silane modified polyether hot-melt adhesive composition and preparation method thereof | |
| CN112375530B (en) | Polyurethane composition with reduced foaming and matte effect | |
| CN101768409A (en) | Double-composition polyurethane waterproof paint and preparation method thereof | |
| CN116162434A (en) | Epoxy modified low-VOC (volatile organic compound) double-component polyurethane adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190929 Address after: 516267 Honghai Fine Chemical Base, Yonghu Town, Huiyang District, Huizhou City, Guangdong Province Applicant after: GUANGDONG SHENGYE CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 523660 Dongfeng East Road, Qingxi Town, Dongguan City, Guangdong Province Applicant before: GUANGDONG PUSTAR ADHESIVES & SEALANTS CO.,LTD. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190723 |