CN107083173B - A kind of anti impact polyurethane cold coating and preparation method thereof - Google Patents
A kind of anti impact polyurethane cold coating and preparation method thereof Download PDFInfo
- Publication number
- CN107083173B CN107083173B CN201710450890.XA CN201710450890A CN107083173B CN 107083173 B CN107083173 B CN 107083173B CN 201710450890 A CN201710450890 A CN 201710450890A CN 107083173 B CN107083173 B CN 107083173B
- Authority
- CN
- China
- Prior art keywords
- added
- stirred
- weight
- polyurethane
- insulated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3891—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having sulfur in addition to phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Organic Insulating Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of anti impact polyurethane cold coatings, it is made of the polyurethane polymer that weight ratio is 2-3:1 and curing agent, the polymer solution of the phosphorylation is mixed with carboxylated basic zirconium phosphate hard filler, it is added in the crosslinking alcohol dispersion liquid that divinylbenzene is raw material, hard filler is effectively distributed in polymeric matrix, reunion is effectively reduced, the surface hardness and impact strength of finished product film are improved.
Description
Technical field
The invention belongs to paint fields, and in particular to a kind of anti impact polyurethane cold coating and preparation method thereof.
Background technique
Polyurethane is a kind of emerging high-molecular organic material, is known as " the fifth-largest plastics ", due to the performance of its brilliance
It is widely used in national economy various fields.Product applications are related to light industry, chemical industry, electronics, weaving, medical treatment, build, build
Material, automobile, national defence, space flight, aviation etc. are widely used high molecular materials, mainly there is polyurethane foam plastics, polyurethane bullet
Property body, polyurethane waterproof material, polyurethane coating, adhesive for polyurethane and polyurethane bio-medical material etc., polyurethane has
Good physical and mechanical properties, hardness range is wide, intensity is high, has wear-resisting, oil resistant, resistant to chemical etching, tear-resistant, resistance to smelly
Oxygen, radiation hardness, damping capaicty are strong, adhesion is good, processing method is various, are all widely used in many industrial circles；
The application field of polyurethane coating mainly has: vehicle paintwork, timber, building coating, anticorrosive coating, flies at ship
Machine, plastics, rubber, external coating of leather etc..Aqueous polyurethane coating be using water as main medium, have low VOC content,
Low or non-environmental-pollution, it is easy for construction the features such as, be one of main substitute of solvent based coating.It is obtained extensively in many fields
General application, such as: woodcare paint and wood floor paint；Paper coating；Building coating；Leather coating；Fabric coating etc.；
However in order to improve polyurethane coating to the protecting effect of substrate, its surface shock resistance is improved, often wherein
Various inorganic fillers are added, the poor compatibility of these inorganic fillers and polymer be easy to cause reunion, reduces the steady of finished product film
It is qualitative；
Application number 201510277294.7 discloses a kind of polyurethane water-proof paint, is made of the raw material of following parts by weight:
30-40 parts of aqueous polyurethane, 20-30 parts of isophorone diisocyanate, 15-25 parts of polyethylene wax, 2-8 parts of carbon black, lemon
2-8 parts of lemon acid, 10-20 parts of Hard PVC, 1-5 parts of potassium silicate, 1.2-2 parts of ethyl acetate, two fourth of phthalic acid
0.4-0.8 parts of ester, 0.4-0.8 parts of bentonite and 10-20 parts of water, production stage are as follows: according to formula quantity by various former materials
Expect that accurate measurement is spare, using cantilever double-spiral conical mixer, raw material is sequentially added according to the sequence of formula, in room
Temperature in the environment of relative air humidity is less than 60%, is stirred 15-20 minutes, is stirred evenly through detection；Comparison text
In part, it joined carbon black as inorganic filler, in preparation method, only carbon black be directly mixed with each raw material, in this way
It is be easy to cause reunion, reduces the stability_intensity of finished product coating.
Many applications, such as external wall, riot shield, canopy are used for high impact properties coating.It represents
Property optically transparent plastic material include diethylene glycol (DEG) two (allyl carbonate), it is plexiglass, poly-
Styrene resin and polycarbonate resin.However, diethylene glycol (DEG) two (allyl carbonate), plexiglass
There is unacceptable impact strength and cracking resistance with polystyrene resin, although polycarbonate resin is shown preferably sometimes
Impact strength and cracking resistance, but it also suffers from that optical property is insufficient and chemical resistance, solvent resistance and Scratch Resistance
It is poor.Hence it is highly desirable to have excellent impact strength.
Summary of the invention
It is an object of the invention to the poor compatibility for inorganic filler and polymer in the prior art, the groups of be easy to causeing
Poly-, the problem of reducing the stability of finished product film, provides a kind of anti impact polyurethane cold coating and preparation method thereof.
To achieve the above object, the invention adopts the following technical scheme:
A kind of anti impact polyurethane cold coating, it is the polyurethane polymer and curing agent group for being 2-3:1 by weight ratio
At.
The polyurethane polymer is made of the raw material of following weight parts:
T-octyl phenoxy group polyethylene ethoxy ethanol 2-4, tetrakis hydroxymetyl phosphonium sulfuric 1-2,2- mercapto benzimidazole
0.3-1, divinylbenzene 0.7-1, alkenyl succinic anhydride 2-4, polycarbonate glycol 100-110, isophorone diisocyanate
70-90, catalyst 3-4, eight water oxygen zirconium chloride 16-20, beta-hydroxy alkylamide 0.4-1, phosphatase 24-6.
The catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl ester according to
2:1 parts by weight of composition.
The preparation method of the polyurethane polymer the following steps are included:
(1) 2- mercapto benzimidazole is taken, is added in the dehydrated alcohol of 14-20 times of its weight, stirs evenly, increases temperature
Degree is 57-60 DEG C, and insulated and stirred 4-10 minutes, divinylbenzene and vinyltriethoxysilane is added, stirs to room temperature, obtains
It is crosslinked alcohol dispersion liquid；
(2) alkenyl succinic anhydride is taken, is added in the deionized water of 20-30 times of its weight, stirs evenly, increasing temperature is
70-75 DEG C, eight water oxygen zirconium chlorides are added, stir evenly, phosphoric acid is added, insulated and stirred 2-3 hours, filtering washed precipitating, often
Temperature is dry, obtains carboxylated hard filler；
(3) catalyst is taken, is added in the acetone of 20-30 times of its weight, stirs evenly；
(4) it takes tetrakis hydroxymetyl phosphonium sulfuric, mixed with polycarbonate glycol, t-octyl phenoxy group polyethylene ethoxy ethanol,
It is heated to 110-120 DEG C, decompression water removal 1-2h mixes with isophorone diisocyanate, is sent in reaction kettle, is passed through nitrogen
Gas, adjusting temperature of reaction kettle is 80-85 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, insulated and stirred 3-4 hours, obtains prepolymerization
Lotion；
(5) above-mentioned carboxylated hard filler is added in prepolymerization lotion, is stirred evenly, crosslinking alcohol dispersion liquid is added,
Increasing temperature is 70-75 DEG C, insulated and stirred 2-3 hours, beta-hydroxy alkylamide is added, 300-400 turns/part stirring 1-2 hours, mistake
Filter, precipitating is washed, and 20-40 minutes are dried at 90-95 DEG C of vacuum to get the polyurethane polymer.
The curing agent be by weight ratio the dimethythiotoluene diamine of 6-8:0.3-1:0.5-1, zinc ricinate,
Calcium stearate mixing composition.
Advantages of the present invention:
The present invention using eight water oxygen zirconium chlorides as presoma, by the reactant aqueous solution with phosphoric acid, then passes through alkenyl first
Succinic anhydride processing, obtains carboxylated basic zirconium phosphate hard filler, then uses polycarbonate glycol, isophorone diisocyanate
For mix monomer, it is polymerize under the action of catalyst, introduces tetrakis hydroxymetyl phosphonium sulfuric in the course of the polymerization process, obtains phosphorylation
Then the polymer solution of the phosphorylation is mixed with carboxylated basic zirconium phosphate hard filler, is added to divinyl by polymer solution
Base benzene is effectively to be distributed to hard filler in polymeric matrix, the group of effectively reducing in the crosslinking alcohol dispersion liquid of raw material
It is poly-, improve the surface hardness and impact strength of finished product film.
Specific embodiment
Embodiment 1
A kind of anti impact polyurethane cold coating, it is made of the polyurethane polymer that weight ratio is 3:1 and curing agent
's.
The polyurethane polymer is made of the raw material of following weight parts:
T-octyl phenoxy group polyethylene ethoxy ethanol 4, tetrakis hydroxymetyl phosphonium sulfuric 2,2- mercapto benzimidazole 1, diethyl
Alkenyl benzene 1, alkenyl succinic anhydride 4, polycarbonate glycol 110, isophorone diisocyanate 90, catalyst 4, eight water oxygen chlorinations
Zirconium 20, beta-hydroxy alkylamide 1, phosphoric acid 6 and vinyltriethoxysilane 1.
The catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl ester according to
2:1。
The preparation method of the polyurethane polymer the following steps are included:
(1) 2- mercapto benzimidazole is taken, is added in the dehydrated alcohol of 20 times of its weight, stirs evenly, increases temperature
It is 60 DEG C, insulated and stirred 10 minutes, divinylbenzene and vinyltriethoxysilane 1 is added, stirs to room temperature, obtains crosslinking alcohol
Dispersion liquid；
(2) alkenyl succinic anhydride is taken, is added in the deionized water of 30 times of its weight, stirs evenly, increasing temperature is 75
DEG C, eight water oxygen zirconium chlorides are added, stir evenly, phosphoric acid is added, insulated and stirred 3 hours, filtering washed precipitating, air drying,
Obtain carboxylated hard filler；
(3) catalyst is taken, is added in the acetone of 30 times of its weight, stirs evenly；
(4) it takes tetrakis hydroxymetyl phosphonium sulfuric, mixed with polycarbonate glycol, t-octyl phenoxy group polyethylene ethoxy ethanol,
120 DEG C are heated to, decompression water removal 2h mixes with isophorone diisocyanate, is sent in reaction kettle, be passed through nitrogen, adjusts
Temperature of reaction kettle is 85 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, insulated and stirred 4 hours, obtains prepolymerization lotion；
(5) above-mentioned carboxylated hard filler is added in prepolymerization lotion, is stirred evenly, crosslinking alcohol dispersion liquid is added,
Increasing temperature is 75 DEG C, and insulated and stirred 3 hours, beta-hydroxy alkylamide is added, and 400 turns/part stir 2 hours, and filtering will precipitate water
It washes, 40 minutes is dried at 95 DEG C of vacuum to get the polyurethane polymer.
The curing agent is mixed by dimethythiotoluene diamine, zinc ricinate, calcium stearate that weight ratio is 8:1:1
It is combined into.
Embodiment 2
A kind of anti impact polyurethane cold coating is made of polyurethane polymer and curing agent that weight ratio is 2:1.
The polyurethane polymer is made of the raw material of following weight parts:
T-octyl phenoxy group polyethylene ethoxy ethanol 2, tetrakis hydroxymetyl phosphonium sulfuric 1,2- mercapto benzimidazole 0.3, two
Vinyl benzene 0.7, alkenyl succinic anhydride 2, polycarbonate glycol 100, isophorone diisocyanate 70, catalyst 3, eight water oxygens
Zirconium chloride 16, beta-hydroxy alkylamide 0.4, phosphatase 24 and vinyltriethoxysilane 1.
The catalyst is that catalyst is cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu uncle 1-
Butyl ester is according to 2:1.
The preparation method of the polyurethane polymer the following steps are included:
(1) 2- mercapto benzimidazole is taken, is added in the dehydrated alcohol of 14 times of its weight, stirs evenly, increases temperature
It is 57 DEG C, insulated and stirred 4 minutes, divinylbenzene and vinyltriethoxysilane 1 is added, stirs to room temperature, obtains crosslinking alcohol
Dispersion liquid；
(2) alkenyl succinic anhydride is taken, is added in the deionized water of 20 times of its weight, stirs evenly, increasing temperature is 70
DEG C, eight water oxygen zirconium chlorides are added, stir evenly, phosphoric acid is added, insulated and stirred 2 hours, filtering washed precipitating, air drying,
Obtain carboxylated hard filler；
(3) catalyst is taken, is added in the acetone of 20 times of its weight, stirs evenly；
(4) it takes tetrakis hydroxymetyl phosphonium sulfuric, mixed with polycarbonate glycol, t-octyl phenoxy group polyethylene ethoxy ethanol,
110 DEG C are heated to, decompression water removal 1h mixes with isophorone diisocyanate, is sent in reaction kettle, be passed through nitrogen, adjusts
Temperature of reaction kettle is 80 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, insulated and stirred 3 hours, obtains prepolymerization lotion；
(5) above-mentioned carboxylated hard filler is added in prepolymerization lotion, is stirred evenly, crosslinking alcohol dispersion liquid is added,
Increasing temperature is 70 DEG C, and insulated and stirred 2 hours, beta-hydroxy alkylamide is added, and 300 turns/part stir 1 hour, and filtering will precipitate water
It washes, 20 minutes is dried at 90 DEG C of vacuum to get the polyurethane polymer.
The curing agent is dimethythiotoluene diamine, zinc ricinate, the stearic acid for being 6:0.3:0.5 by weight ratio
Calcium mixing composition.
Embodiment 3
A kind of anti impact polyurethane cold coating, it is made of the polyurethane polymer that weight ratio is 2:1 and curing agent
's.
The polyurethane polymer is made of the raw material of following weight parts:
T-octyl phenoxy group polyethylene ethoxy ethanol 2, tetrakis hydroxymetyl phosphonium sulfuric 1,2- mercapto benzimidazole 0.5, two
Vinyl benzene 0.7, alkenyl succinic anhydride 2, polycarbonate glycol 104, isophorone diisocyanate 75, catalyst 3, eight water oxygens
Zirconium chloride 16, beta-hydroxy alkylamide 0.7, phosphatase 24 and vinyltriethoxysilane 1.
The catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl ester according to
2:1。
The preparation method of the polyurethane polymer the following steps are included:
(1) 2- mercapto benzimidazole is taken, is added in the dehydrated alcohol of 14 times of its weight, stirs evenly, increases temperature
It is 57 DEG C, insulated and stirred 5 minutes, divinylbenzene is added, stirs to room temperature, alcohol dispersion liquid must be crosslinked；
(2) alkenyl succinic anhydride is taken, is added in the deionized water of 22 times of its weight, stirs evenly, increasing temperature is 70
DEG C, eight water oxygen zirconium chlorides are added, stir evenly, phosphoric acid is added, insulated and stirred 2 hours, filtering washed precipitating, air drying,
Obtain carboxylated hard filler；
(3) catalyst is taken, is added in the acetone of 28 times of its weight, stirs evenly；
(4) it takes tetrakis hydroxymetyl phosphonium sulfuric, mixed with polycarbonate glycol, t-octyl phenoxy group polyethylene ethoxy ethanol,
110 DEG C are heated to, decompression water removal 1h mixes with isophorone diisocyanate, is sent in reaction kettle, be passed through nitrogen, adjusts
Temperature of reaction kettle is 81 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, insulated and stirred 3 hours, obtains prepolymerization lotion；
(5) above-mentioned carboxylated hard filler is added in prepolymerization lotion, is stirred evenly, crosslinking alcohol dispersion liquid is added,
Increasing temperature is 70 DEG C, insulated and stirred 2 hours, beta-hydroxy alkylamide is added, 300-400 turns/part stirring 1 hour, and filtering will sink
It forms sediment and washes, 20 minutes are dried at 90 DEG C of vacuum to get the polyurethane polymer.
It is 7:0.5:0.8 dimethythiotoluene diamine, zinc ricinate, calcium stearate that the curing agent, which is by weight ratio,
Mixing composition.
Embodiment 4
A kind of anti impact polyurethane cold coating, it is made of the polyurethane polymer that weight ratio is 2:1 and curing agent
's.
The polyurethane polymer is made of the raw material of following weight parts:
T-octyl phenoxy group polyethylene ethoxy ethanol 2, tetrakis hydroxymetyl phosphonium sulfuric 1,2- mercapto benzimidazole 0.5, two
Vinyl benzene 0.7, alkenyl succinic anhydride 2, polycarbonate glycol 105, isophorone diisocyanate 75, catalyst 3, eight water oxygens
Zirconium chloride 16, beta-hydroxy alkylamide 0.7, phosphatase 24 and vinyltriethoxysilane 1.
The catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl ester according to
2:1。
The preparation method of the polyurethane polymer the following steps are included:
(1) 2- mercapto benzimidazole is taken, is added in the dehydrated alcohol of 18 times of its weight, stirs evenly, increases temperature
It is 57 DEG C, insulated and stirred 5 minutes, divinylbenzene is added, stirs to room temperature, alcohol dispersion liquid must be crosslinked；
(2) alkenyl succinic anhydride is taken, is added in the deionized water of 22 times of its weight, stirs evenly, increasing temperature is 72
DEG C, eight water oxygen zirconium chlorides are added, stir evenly, phosphoric acid is added, insulated and stirred 2 hours, filtering washed precipitating, air drying,
Obtain carboxylated hard filler；
(3) catalyst is taken, is added in the acetone of 25 times of its weight, stirs evenly；
(4) it takes tetrakis hydroxymetyl phosphonium sulfuric, mixed with polycarbonate glycol, t-octyl phenoxy group polyethylene ethoxy ethanol,
It is heated to 110-120 DEG C, decompression water removal 1h mixes with isophorone diisocyanate, is sent in reaction kettle, is passed through nitrogen,
Adjusting temperature of reaction kettle is 81 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, insulated and stirred 3 hours, obtains prepolymerization lotion；
(5) above-mentioned carboxylated hard filler is added in prepolymerization lotion, is stirred evenly, crosslinking alcohol dispersion liquid is added,
Increasing temperature is 75 DEG C, and insulated and stirred 2 hours, beta-hydroxy alkylamide is added, and 300 turns/part stir 1 hour, and filtering will precipitate water
It washes, 20 minutes is dried at 92 DEG C of vacuum to get the polyurethane polymer.
The curing agent is dimethythiotoluene diamine, zinc ricinate, the stearic acid for being 6:0.5:0.8 by weight ratio
Calcium mixing composition.
Performance test:
Shock resistance is tested according to GB/T 1732-93(paint film impact resistance measuring method) it is tested, surface hardness is adopted
What is taken is that JIS K 5400-90-84 is tested.
1 performance test of table
| Example 1 | Example 2 | Example 3 | Example 4 | Conventional polyurethanes | |
| Impact strength/kg.cm | 27.9 | 28.9 | 29.8 | 35.6 | 18.9 |
| Tensile strength/Mpa | 7.2 | 7.6 | 6.7 | 6.3 | 4.5 |
| Surface hardness | 7H | 6H | 6H | 5H | F |
Table 2 is not plus the film performance of crosslinking alcohol is tested
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Impact strength/kg.cm | 22.1 | 26.9 | 27.6 | 22.7 |
| Surface hardness | 3H | 3H | 3H | 1H |
Table 3 is not plus the film performance of N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl ester is tested
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Impact strength/kg.cm | 24.2 | 23.2 | 24.3 | 21.9 |
| Surface hardness | 7H | 5H | 5H | 4H |
Table 4 is not plus the film performance of catalyst is tested
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Impact strength/kg.cm | 19.2 | 18.7 | 20,3 | 20.6 |
| Surface hardness | 6H | 6H | 6H | 4H |
As needed for length and its protection right, other raw materials detection data applicant involved in the present invention arrived is with regard to different
One lists.
According to the present invention not add certain raw material (namely blank test), people from this field should be clear that understanding, then
This is not explained one by one.
Claims (3)
1. a kind of anti impact polyurethane cold coating, which is characterized in that it be by weight ratio be 2-3:1 polyurethane polymer and
Curing agent composition, what the polyurethane polymer was made of the raw material of following weight parts:
T-octyl phenoxy group polyethylene ethoxy ethanol 2-4, tetrakis hydroxymetyl phosphonium sulfuric 1-2,2- mercapto benzimidazole 0.3-1,
Divinylbenzene 0.7-1, alkenyl succinic anhydride 2-4, polycarbonate glycol 100-110, isophorone diisocyanate 70-90,
Catalyst 3-4, eight water oxygen zirconium chloride 16-20, beta-hydroxy alkylamide 0.4-1, phosphatase 24-6, vinyltriethoxysilane 1, institute
State the preparation method of polyurethane polymer the following steps are included:
(1) 2- mercapto benzimidazole is taken, is added in the dehydrated alcohol of 14-20 times of its weight, stirs evenly, increasing temperature is
57-60 DEG C, insulated and stirred 4-10min, divinylbenzene and vinyltriethoxysilane is added, stirs to room temperature, must be crosslinked
Alcohol dispersion liquid；
(2) alkenyl succinic anhydride is taken, is added in the deionized water of 20-30 times of its weight, stirs evenly, raising temperature is 70-
75 DEG C, eight water oxygen zirconium chlorides are added, stir evenly, phosphoric acid is added, insulated and stirred 2-3 hours, filtering washed precipitating, room temperature
It is dry, obtain carboxylated hard filler；
(3) catalyst is taken, is added in the acetone of 20-30 times of its weight, stirs evenly；
(4) it takes tetrakis hydroxymetyl phosphonium sulfuric, mixed with polycarbonate glycol, t-octyl phenoxy group polyethylene ethoxy ethanol, heated
To 110-120 DEG C, decompression water removal 1-2h mixes with isophorone diisocyanate, is sent in reaction kettle, be passed through nitrogen, adjusts
Saving temperature of reaction kettle is 80-85 DEG C, the acetone soln of above-mentioned catalyst is added dropwise, insulated and stirred 3-4h obtains prepolymerization lotion；
(5) above-mentioned carboxylated hard filler is added in prepolymerization lotion, is stirred evenly, crosslinking alcohol dispersion liquid is added, increases
Temperature is 70-75 DEG C, insulated and stirred 2-3h, and beta-hydroxy alkylamide is added, and 300-400 turns/part stirring 1-2 hours, and filtering will sink
It forms sediment and washes, dry 20-40min is at 90-95 DEG C of vacuum to get the polyurethane polymer.
2. a kind of anti impact polyurethane cold coating according to claim 1, which is characterized in that the catalyst was
Diisopropylbenzene (DIPB) and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl ester are aoxidized according to 2:1 parts by weight of composition.
3. a kind of anti impact polyurethane cold coating according to claim 1, which is characterized in that the curing agent be by
Dimethythiotoluene diamine, zinc ricinate, calcium stearate the mixing composition that weight ratio is 6-8:0.3-1:0.5-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710450890.XA CN107083173B (en) | 2017-06-15 | 2017-06-15 | A kind of anti impact polyurethane cold coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710450890.XA CN107083173B (en) | 2017-06-15 | 2017-06-15 | A kind of anti impact polyurethane cold coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107083173A CN107083173A (en) | 2017-08-22 |
| CN107083173B true CN107083173B (en) | 2019-02-26 |
Family
ID=59605777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710450890.XA Active CN107083173B (en) | 2017-06-15 | 2017-06-15 | A kind of anti impact polyurethane cold coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107083173B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107384173A (en) * | 2017-08-30 | 2017-11-24 | 霍邱金木鱼农业科技有限公司 | A kind of hard polyurethane ester paint and preparation method thereof |
| CN107502114B (en) * | 2017-09-05 | 2020-04-14 | 弋阳县中泰君诺新材料有限公司 | Interior wall water-based paint for formaldehyde adsorption and preparation method thereof |
| CN108598536A (en) * | 2018-04-27 | 2018-09-28 | 芜湖天科生物科技有限公司 | A kind of heat-resisting proton exchange membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471547A (en) * | 2000-09-22 | 2004-01-28 | PPG��ҵ����˾ | Curable polyurethanes, coatings prepared therefrom, and method of making the same |
| CN1606578A (en) * | 2000-09-22 | 2005-04-13 | Ppg工业俄亥俄公司 | Curable polyurethanes, coatings prepared therefrom, and method of making the same |
| CN103614045A (en) * | 2009-10-29 | 2014-03-05 | 关西涂料株式会社 | Copolymer, aqueous coating composition containing copolymer, and method for forming multilayer coating film |
| CN107083176A (en) * | 2017-06-08 | 2017-08-22 | 苏州蓝锐纳米科技有限公司 | A kind of polyurethane mirror surface coating and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5585957B2 (en) * | 2010-08-12 | 2014-09-10 | 東海カーボン株式会社 | Polyurethane resin-added pigment, method for producing polyurethane resin-added pigment, pigment dispersion composition, and inkjet ink composition |
-
2017
- 2017-06-15 CN CN201710450890.XA patent/CN107083173B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471547A (en) * | 2000-09-22 | 2004-01-28 | PPG��ҵ����˾ | Curable polyurethanes, coatings prepared therefrom, and method of making the same |
| CN1606578A (en) * | 2000-09-22 | 2005-04-13 | Ppg工业俄亥俄公司 | Curable polyurethanes, coatings prepared therefrom, and method of making the same |
| CN103614045A (en) * | 2009-10-29 | 2014-03-05 | 关西涂料株式会社 | Copolymer, aqueous coating composition containing copolymer, and method for forming multilayer coating film |
| CN107083176A (en) * | 2017-06-08 | 2017-08-22 | 苏州蓝锐纳米科技有限公司 | A kind of polyurethane mirror surface coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107083173A (en) | 2017-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4971837A (en) | Chip resistant coatings and methods of application | |
| CN107083173B (en) | A kind of anti impact polyurethane cold coating and preparation method thereof | |
| US5066733A (en) | Chip resistant coatings and methods of application | |
| AU652704B2 (en) | One package stable etch resistant coating | |
| CA2160777C (en) | Color-clear composite coatings having improved intercoat adhesion | |
| CN106381043B (en) | Water-based two-component polyurethane primer coating and preparation method thereof | |
| CN107163217B (en) | Preparation method of nano-diamond modified waterborne polyurethane | |
| CN107083176A (en) | A kind of polyurethane mirror surface coating and preparation method thereof | |
| CN110499094B (en) | Graphene-modified waterborne polyurethane anticorrosive paint and preparation method thereof | |
| CN108299618A (en) | A kind of high-performance water-based UV solidified resins and preparation method thereof | |
| KR101362523B1 (en) | Low-voc primer for plastic coating | |
| JPS6044561A (en) | Rapidly-drying coating composition | |
| CN103666179A (en) | VOC (volatile organic compound)-free epoxy modified water-borne PU (polyurethane) finish paint and preparation method thereof | |
| CN107083178B (en) | A kind of antifriction polyurethane coating and preparation method thereof | |
| CN108727934B (en) | High-solids coating composition and coating method using same | |
| Khorgami et al. | Polyurethanes for Corrosion Protective Coatings | |
| EP0813552B1 (en) | Modified acryl copolymer | |
| US6084036A (en) | Carboxyl-functional adduct from oh- or epoxy-functional polymer and citric acid (anhydride) with anhydride | |
| CN103087621A (en) | Antibacterial waterborne polyurethane wood lacquer | |
| CN107043590A (en) | A kind of anti-corrosion polyurethane coating | |
| CN107384173A (en) | A kind of hard polyurethane ester paint and preparation method thereof | |
| CN103059709B (en) | A kind of waterborne polyurethane wood coatings with antibacterial effect | |
| CA2893284A1 (en) | Alpha, omega-hydroxy-functionalized oligoester as adhesion promoter in aqueous basecoats | |
| CN103113816B (en) | A kind of preparation method with the waterborne polyurethane wood coatings of antibacterial effect | |
| JP2009249573A (en) | Aqueous primer for lamp reflector, production method of aqueous primer for lamp reflector, and lamp reflector |
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: 20190118 Address after: 463400 the southern side of pioneering five road, Pingyu County, Zhumadian, Henan Applicant after: Henan Central Branch Lanling waterproof materials Co Ltd Address before: 264006 Yantai Wanhua Polyurethane Co., Ltd. No. 47 Zhujiang Road, Yantai Development Zone, Shandong Province Applicant before: Duan Xiaoning |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |