CN107083173A - 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
- CN107083173A CN107083173A CN201710450890.XA CN201710450890A CN107083173A CN 107083173 A CN107083173 A CN 107083173A CN 201710450890 A CN201710450890 A CN 201710450890A CN 107083173 A CN107083173 A CN 107083173A
- Authority
- CN
- China
- Prior art keywords
- stirred
- added
- polyurethane
- weight
- 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.)
- Granted
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 coating, it by weight ratio is 23 that it, which is,:1 polyurethane polymer and curing agent composition, 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 case hardness and impact strength of finished product film is improved.
Description
Technical field
The invention belongs to paint field, and in particular to a kind of anti impact polyurethane cold coating and preparation method thereof.
Background technology
Polyurethane is a kind of emerging high-molecular organic material, is described as " the fifth-largest plastics ", because of its remarkable performance
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 polymer 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, with wear-resisting, oil resistant, resistant to chemical etching, tear-resistant, resistance to smelly
Oxygen, radiation hardness, damping capaicty are strong, adhesion is good, processing mode is various, are all widely used in many industrial circles；
The application field of polyurethane coating mainly has：Vehicle paintwork, ship, timber, building application, anticorrosive coating, aircraft, modeling
Material, rubber, external coating of leather etc..Aqueous polyurethane coating be using water as main medium, with low VOC content, it is low or
The features such as non-environmental-pollution, easy construction, be one of main substitute of solvent based coating.Obtained widely in many fields
Using such as：Woodcare paint and wood floor paint；Paper coating；Building coating；Leather coating；Fabric coating etc.；
But in order to improve protecting effect of the polyurethane coating to base material, improve its surface shock resistance, often add wherein
The poor compatibility of various inorganic fillers, these inorganic fillers and polymer, easily causes reunion, reduces the stabilization of finished product film
Property；
Application number 201510277294.7, discloses a kind of polyurethane water-proof paint, is made up of the raw material of following parts by weight：Water
30-40 parts of polyurethane of property, 20-30 parts of IPDI, 15-25 parts of Tissuemat E, 2-8 parts of carbon black, lemon
Sour 2-8 parts, 10-20 parts of RPVC, 1-5 parts of potassium silicate, 1.2-2 parts of ethyl acetate, dibutyl phthalate
10-20 parts of 0.4-0.8 parts, 0.4-0.8 parts of bentonite and water, production stage is：According to formula quantity by various raw material
Accurate measurement is standby, and using cantilever double-spiral conical mixer, raw material are sequentially added according to the order of formula, in room temperature,
Relative air humidity is less than in the environment of 60%, stirs 15-20 minutes, stirs after testing, you can；The documents
In, carbon black is added as inorganic filler, in its preparation method, is simply directly mixed carbon black with each raw material, so appearance
Reunion is easily caused, the stability_intensity of finished product coating is reduced.
It is used for many applications, such as external wall, riot shield, canopy with high impact properties coating.Represent
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 not enough and chemical resistance, solvent resistance and Scratch Resistance
It is poor.Hence it is highly desirable to have excellent impact strength.
The content of the invention
It is an object of the invention to the poor compatibility for inorganic filler in the prior art and polymer, the group of easily causing
Poly-, there is provided a kind of anti impact polyurethane cold coating and preparation method thereof for the problem of reducing the stability of finished product film.
To achieve the above object, the present invention uses following technical scheme：
A kind of anti impact polyurethane cold coating, it be by weight ratio be 2-3:1 polyurethane polymer and curing agent composition.
Described polyurethane polymer is made up 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, PCDL 100-110, IPDI 70-90,
Catalyst 3-4, eight water oxygen zirconium chloride 16-20, beta-hydroxy alkylamide 0.4-1, phosphatase 24-6.
Described catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl esters according to
2:1 parts by weight of composition.
The preparation method of the polyurethane polymer comprises the following steps：
（1）Take in 2- mercapto benzimidazoles, the absolute ethyl alcohol for being added to 14-20 times of its weight, stir, rise temperature is
57-60 DEG C, insulated and stirred 4-10 minutes adds divinylbenzene and VTES, stirs to normal temperature, must be crosslinked
Alcohol dispersion liquid；
（2）Alkenyl succinic anhydride is taken, in the deionized water for being added to 20-30 times of its weight, is stirred, rise temperature is 70-
75 DEG C, eight water oxygen zirconium chlorides are added, are stirred, add phosphoric acid, insulated and stirred 2-3 hours, filtering washes precipitation, normal temperature
Dry, obtain carboxylated hard filler；
（3）Catalyst is taken, in the acetone for being added to 20-30 times of its weight, is stirred；
（4）Take tetrakis hydroxymetyl phosphonium sulfuric, mixed with PCDL, t-octyl phenoxy group polyethylene ethoxy ethanol, heated
To 110-120 DEG C, decompression water removal 1-2h mixes with IPDI, is sent in reactor, be passed through nitrogen, adjusts
It is 80-85 DEG C to save temperature of reaction kettle, and the acetone soln of above-mentioned catalyst is added dropwise, and insulated and stirred 3-4 hours obtains prepolymerization emulsion；
（5）Above-mentioned carboxylated hard filler is added in prepolymerization emulsion, stirred, crosslinking alcohol dispersion liquid, rise is added
Temperature is 70-75 DEG C, insulated and stirred 2-3 hours, adds beta-hydroxy alkylamide, and 300-400 turns/part is stirred 1-2 hours, filtering,
Precipitation is washed, is dried 20-40 minutes at 90-95 DEG C of vacuum, produces the polyurethane polymer.
Described curing agent be by weight ratio be 6-8:0.3-1：0.5-1 dimethythiotoluene diamine, zinc ricinate,
Calcium stearate mixing composition.
Advantages of the present invention：
The present invention, by the reactant aqueous solution with phosphoric acid, then passes through alkenyl succinate first using eight water oxygen zirconium chlorides as presoma
Acid anhydrides processing, obtains carboxylated basic zirconium phosphate hard filler, it is mixed then to use PCDL, IPDI
Monomer is closed, is polymerize under catalyst action, tetrakis hydroxymetyl phosphonium sulfuric is introduced in the course of the polymerization process, obtain the polymerization of phosphorylation
Thing solution, then the polymer solution of the phosphorylation is mixed, be added to divinylbenzene with carboxylated basic zirconium phosphate hard filler
In the crosslinking alcohol dispersion liquid of raw material, hard filler to be effectively distributed in polymeric matrix, reunion is effectively reduced, carries
The high case hardness and impact strength of finished product film.
Embodiment
Embodiment 1
A kind of anti impact polyurethane cold coating, it be by weight ratio be 3:1 polyurethane polymer and curing agent composition.
Described polyurethane polymer is made up of the raw material of following weight parts：
T-octyl phenoxy group polyethylene ethoxy ethanol 4, tetrakis hydroxymetyl phosphonium sulfuric 2,2- mercaptos benzimidazole 1, divinyl
Benzene 1, alkenyl succinic anhydride 4, PCDL 110, IPDI 90, catalyst 4, eight water oxygen zirconium chlorides
20th, beta-hydroxy alkylamide 1, phosphoric acid 6 and VTES 1.
Described catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl esters according to
2:1。
The preparation method of the polyurethane polymer comprises the following steps：
（1）2- mercapto benzimidazoles are taken, in the absolute ethyl alcohol for being added to 20 times of its weight, are stirred, rise temperature is 60
DEG C, insulated and stirred 10 minutes adds divinylbenzene and VTES 1, stirs to normal temperature, must be crosslinked alcohol and disperse
Liquid；
（2）Alkenyl succinic anhydride is taken, in the deionized water for being added to 30 times of its weight, is stirred, rise temperature is 75 DEG C, plus
Enter eight water oxygen zirconium chlorides, stir, add phosphoric acid, precipitation is washed in insulated and stirred 3 hours, filtering, and air drying obtains carboxylic
Base hard filler；
（3）Catalyst is taken, in the acetone for being added to 30 times of its weight, is stirred；
（4）Take tetrakis hydroxymetyl phosphonium sulfuric, mixed with PCDL, t-octyl phenoxy group polyethylene ethoxy ethanol, heated
To 120 DEG C, decompression water removal 2h is mixed with IPDI, is sent in reactor, is passed through nitrogen, regulation reaction
Kettle temperature degree is 85 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, and insulated and stirred 4 hours obtains prepolymerization emulsion；
（5）Above-mentioned carboxylated hard filler is added in prepolymerization emulsion, stirred, crosslinking alcohol dispersion liquid, rise is added
Temperature is 75 DEG C, insulated and stirred 3 hours, adds beta-hydroxy alkylamide, and 400 turns/part are stirred 2 hours, and precipitation is washed in filtering,
Dried 40 minutes at 95 DEG C of vacuum, produce the polyurethane polymer.
Described curing agent be by weight ratio be 8:1：1 dimethythiotoluene diamine, zinc ricinate, calcium stearate are mixed
It is combined into.
Embodiment 2
A kind of anti impact polyurethane cold coating, be by weight ratio be 2:1 polyurethane polymer and curing agent composition.
Described polyurethane polymer is made up of the raw material of following weight parts：
T-octyl phenoxy group polyethylene ethoxy ethanol 2, tetrakis hydroxymetyl phosphonium sulfuric 1,2- mercaptos benzimidazole 0.3, divinyl
Base benzene 0.7, alkenyl succinic anhydride 2, PCDL 100, IPDI 70, catalyst 3, eight water oxygen chlorinations
Zirconium 16, beta-hydroxy alkylamide 0.4, phosphatase 24 and VTES 1.
Described 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 comprises the following steps：
（1）2- mercapto benzimidazoles are taken, in the absolute ethyl alcohol for being added to 14 times of its weight, are stirred, rise temperature is 57
DEG C, insulated and stirred 4 minutes adds divinylbenzene and VTES 1, stirs to normal temperature, must be crosslinked alcohol and disperse
Liquid；
（2）Alkenyl succinic anhydride is taken, in the deionized water for being added to 20 times of its weight, is stirred, rise temperature is 70 DEG C, plus
Enter eight water oxygen zirconium chlorides, stir, add phosphoric acid, precipitation is washed in insulated and stirred 2 hours, filtering, and air drying obtains carboxylic
Base hard filler；
（3）Catalyst is taken, in the acetone for being added to 20 times of its weight, is stirred；
（4）Take tetrakis hydroxymetyl phosphonium sulfuric, mixed with PCDL, t-octyl phenoxy group polyethylene ethoxy ethanol, heated
To 110 DEG C, decompression water removal 1h is mixed with IPDI, is sent in reactor, is passed through nitrogen, regulation reaction
Kettle temperature degree is 80 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, and insulated and stirred 3 hours obtains prepolymerization emulsion；
（5）Above-mentioned carboxylated hard filler is added in prepolymerization emulsion, stirred, crosslinking alcohol dispersion liquid, rise is added
Temperature is 70 DEG C, insulated and stirred 2 hours, adds beta-hydroxy alkylamide, and 300 turns/part are stirred 1 hour, and precipitation is washed in filtering,
Dried 20 minutes at 90 DEG C of vacuum, produce the polyurethane polymer.
Described curing agent be by weight ratio be 6:0.3：0.5 dimethythiotoluene diamine, zinc ricinate, stearic acid
Calcium mixing composition.
Embodiment 3
A kind of anti impact polyurethane cold coating, it be by weight ratio be 2:1 polyurethane polymer and curing agent composition.
Described polyurethane polymer is made up of the raw material of following weight parts：
T-octyl phenoxy group polyethylene ethoxy ethanol 2, tetrakis hydroxymetyl phosphonium sulfuric 1,2- mercaptos benzimidazole 0.5, divinyl
Base benzene 0.7, alkenyl succinic anhydride 2, PCDL 104, IPDI 75, catalyst 3, eight water oxygen chlorinations
Zirconium 16, beta-hydroxy alkylamide 0.7, phosphatase 24 and VTES 1.
Described catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl esters according to
2:1。
The preparation method of the polyurethane polymer comprises the following steps：
（1）2- mercapto benzimidazoles are taken, in the absolute ethyl alcohol for being added to 14 times of its weight, are stirred, rise temperature is 57
DEG C, insulated and stirred 5 minutes adds divinylbenzene, stirs to normal temperature, must be crosslinked alcohol dispersion liquid；
（2）Alkenyl succinic anhydride is taken, in the deionized water for being added to 22 times of its weight, is stirred, rise temperature is 70 DEG C, plus
Enter eight water oxygen zirconium chlorides, stir, add phosphoric acid, precipitation is washed in insulated and stirred 2 hours, filtering, and air drying obtains carboxylic
Base hard filler；
（3）Catalyst is taken, in the acetone for being added to 28 times of its weight, is stirred；
（4）Take tetrakis hydroxymetyl phosphonium sulfuric, mixed with PCDL, t-octyl phenoxy group polyethylene ethoxy ethanol, heated
To 110 DEG C, decompression water removal 1h is mixed with IPDI, is sent in reactor, is passed through nitrogen, regulation reaction
Kettle temperature degree is 81 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, and insulated and stirred 3 hours obtains prepolymerization emulsion；
（5）Above-mentioned carboxylated hard filler is added in prepolymerization emulsion, stirred, crosslinking alcohol dispersion liquid, rise is added
Temperature is 70 DEG C, insulated and stirred 2 hours, adds beta-hydroxy alkylamide, and 300-400 turns/part is stirred 1 hour, and filtering will precipitate water
Wash, dried 20 minutes at 90 DEG C of vacuum, produce the polyurethane polymer.
Described curing agent be by weight ratio be 7:0.5：0.8 dimethythiotoluene diamine, zinc ricinate, calcium stearate
Mixing composition.
Embodiment 4
A kind of anti impact polyurethane cold coating, it be by weight ratio be 2:1 polyurethane polymer and curing agent composition.
Described polyurethane polymer is made up of the raw material of following weight parts：
T-octyl phenoxy group polyethylene ethoxy ethanol 2, tetrakis hydroxymetyl phosphonium sulfuric 1,2- mercaptos benzimidazole 0.5, divinyl
Base benzene 0.7, alkenyl succinic anhydride 2, PCDL 105, IPDI 75, catalyst 3, eight water oxygen chlorinations
Zirconium 16, beta-hydroxy alkylamide 0.7, phosphatase 24 and VTES 1.
Described catalyst be cumyl peroxide and N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl esters according to
2:1。
The preparation method of the polyurethane polymer comprises the following steps：
（1）2- mercapto benzimidazoles are taken, in the absolute ethyl alcohol for being added to 18 times of its weight, are stirred, rise temperature is 57
DEG C, insulated and stirred 5 minutes adds divinylbenzene, stirs to normal temperature, must be crosslinked alcohol dispersion liquid；
（2）Alkenyl succinic anhydride is taken, in the deionized water for being added to 22 times of its weight, is stirred, rise temperature is 72 DEG C, plus
Enter eight water oxygen zirconium chlorides, stir, add phosphoric acid, precipitation is washed in insulated and stirred 2 hours, filtering, and air drying obtains carboxylic
Base hard filler；
（3）Catalyst is taken, in the acetone for being added to 25 times of its weight, is stirred；
（4）Take tetrakis hydroxymetyl phosphonium sulfuric, mixed with PCDL, t-octyl phenoxy group polyethylene ethoxy ethanol, heated
To 110-120 DEG C, decompression water removal 1h mixes with IPDI, is sent in reactor, be passed through nitrogen, adjusts
Temperature of reaction kettle is 81 DEG C, and the acetone soln of above-mentioned catalyst is added dropwise, and insulated and stirred 3 hours obtains prepolymerization emulsion；
（5）Above-mentioned carboxylated hard filler is added in prepolymerization emulsion, stirred, crosslinking alcohol dispersion liquid, rise is added
Temperature is 75 DEG C, insulated and stirred 2 hours, adds beta-hydroxy alkylamide, and 300 turns/part are stirred 1 hour, and precipitation is washed in filtering,
Dried 20 minutes at 92 DEG C of vacuum, produce the polyurethane polymer.
Described curing agent be by weight ratio be 6:0.5：0.8 dimethythiotoluene diamine, zinc ricinate, stearic acid
Calcium mixing composition.
Performance test：
Shock resistance is tested according to GB/T 1732-93（Paint film impact resistance determination method）Tested, what case hardness was taken
It is that JIS K 5400-90-84 are tested.
The performance test of table 1
| 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 |
| Case hardness | 7H | 6H | 6H | 5H | F |
Table 2 does not add the film performance test of crosslinking alcohol
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Impact strength/kg.cm | 22.1 | 26.9 | 27.6 | 22.7 |
| Case hardness | 3H | 3H | 3H | 1H |
Table 3 does not add the film performance test of N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl esters
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Impact strength/kg.cm | 24.2 | 23.2 | 24.3 | 21.9 |
| Case hardness | 7H | 5H | 5H | 4H |
Table 4 does not add the film performance test of catalyst
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Impact strength/kg.cm | 19.2 | 18.7 | 20,3 | 20.6 |
| Case hardness | 6H | 6H | 6H | 4H |
Because other raw materials detection data applicant that needed for length and its protection right, the present invention relates to just does not arrange one by one
Go out.
Involved in the present invention does not add certain raw material（Namely blank test）, people from this area should be clear that understanding, then
This is not explained one by one.
Claims (5)
1. a kind of anti impact polyurethane cold coating, it is characterised in that it by weight ratio is 2-3 that it, which is,:1 polyurethane polymer and
Curing agent composition.
2. a kind of anti impact polyurethane cold coating according to claim 1, it is characterised in that described polyurethane polymerization
Body is made up 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, PCDL 100-110, IPDI 70-90,
Catalyst 3-4, eight water oxygen zirconium chloride 16-20, beta-hydroxy alkylamide 0.4-1, phosphatase 24-6, VTES 1.
3. a kind of anti impact polyurethane cold coating according to claim 2, it is characterised in that described catalyst was
Diisopropylbenzene (DIPB) is aoxidized with N- (9-fluorenylmethyloxycarbonyl)-D-Glu 1- tert-butyl esters according to 2:1 parts by weight of composition.
4. a kind of anti impact polyurethane cold coating according to claim 2,3, it is characterised in that the polyurethane polymerization
The preparation method of body comprises the following steps：
（1）Take in 2- mercapto benzimidazoles, the absolute ethyl alcohol for being added to 14-20 times of its weight, stir, rise temperature is
57-60 DEG C, insulated and stirred 4-10min adds divinylbenzene and VTES, stirs to normal temperature, must be crosslinked
Alcohol dispersion liquid；
（2）Alkenyl succinic anhydride is taken, in the deionized water for being added to 20-30 times of its weight, is stirred, rise temperature is 70-
75 DEG C, eight water oxygen zirconium chlorides are added, are stirred, add phosphoric acid, insulated and stirred 2-3 hours, filtering washes precipitation, normal temperature
Dry, obtain carboxylated hard filler；
（3）Catalyst is taken, in the acetone for being added to 20-30 times of its weight, is stirred；
（4）Take tetrakis hydroxymetyl phosphonium sulfuric, mixed with PCDL, t-octyl phenoxy group polyethylene ethoxy ethanol, heated
To 110-120 DEG C, decompression water removal 1-2h mixes with IPDI, is sent in reactor, be passed through nitrogen, adjusts
It is 80-85 DEG C to save temperature of reaction kettle, and the acetone soln of above-mentioned catalyst is added dropwise, and insulated and stirred 3-4h obtains prepolymerization emulsion；
（5）Above-mentioned carboxylated hard filler is added in prepolymerization emulsion, stirred, crosslinking alcohol dispersion liquid, rise is added
Temperature is 70-75 DEG C, insulated and stirred 2-3h, adds beta-hydroxy alkylamide, and 300-400 turns/part is stirred 1-2 hours, filtering, will be heavy
Form sediment and wash, 20-40min is dried at 90-95 DEG C of vacuum, the polyurethane polymer is produced.
5. a kind of anti impact polyurethane cold coating according to claim 1, it is characterised in that described curing agent be by
Weight ratio is 6-8:0.3-1：0.5-1 dimethythiotoluene diamine, zinc ricinate, calcium stearate mixing are constituted.
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 true CN107083173A (en) | 2017-08-22 |
| CN107083173B 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) |
Cited By (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 |
| CN107502114A (en) * | 2017-09-05 | 2017-12-22 | 霍邱金木鱼农业科技有限公司 | A kind of water paint for internal walls for formaldehyde absorbing 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 (5)
| 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 |
| US20130217826A1 (en) * | 2010-08-12 | 2013-08-22 | Tokai Carbon Co., Ltd. | Polyurethane resin addition pigment, process for producing polyurethane resin addition pigment, pigment dispersion composition, and jet printing ink composition |
| 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 |
-
2017
- 2017-06-15 CN CN201710450890.XA patent/CN107083173B/en active Active
Patent Citations (5)
| 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 |
| US20130217826A1 (en) * | 2010-08-12 | 2013-08-22 | Tokai Carbon Co., Ltd. | Polyurethane resin addition pigment, process for producing polyurethane resin addition pigment, pigment dispersion composition, and jet printing ink composition |
| 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 |
Cited By (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 |
| CN107502114A (en) * | 2017-09-05 | 2017-12-22 | 霍邱金木鱼农业科技有限公司 | A kind of water paint for internal walls for formaldehyde absorbing 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107083173B (en) | 2019-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107083173B (en) | A kind of anti impact polyurethane cold coating and preparation method thereof | |
| CN107163217B (en) | Preparation method of nano-diamond modified waterborne polyurethane | |
| CN106381043B (en) | Water-based two-component polyurethane primer coating and preparation method thereof | |
| CN107083176A (en) | A kind of polyurethane mirror surface coating and preparation method thereof | |
| CN101177479A (en) | Method for preparing self-emulsification aqueous epoxy resin emulsion | |
| CN110499094B (en) | Graphene-modified waterborne polyurethane anticorrosive paint and preparation method thereof | |
| CN101759861A (en) | Method for preparing waterborne polyurethane emulsion capable of self-crosslinking at normal temperature | |
| Ratna | Recent advances and applications of thermoset resins | |
| CN109593454B (en) | Polyurethane coating and preparation method and application thereof | |
| CN108299618A (en) | A kind of high-performance water-based UV solidified resins and preparation method thereof | |
| Lu et al. | Crosslinkable poly (vinyl acetate) emulsions for wood adhesive | |
| CN103666178A (en) | VOC (volatile organic compound)-free high-solid-content water-borne epoxy PU (polyurethane) primer and preparation method thereof | |
| Zhang et al. | Preparation and properties of corrosion-resistant coatings from waterborne polyurethane modified epoxy emulsion | |
| CN103627003A (en) | Flurosilicon graft polymer-grafted epoxy resin and preparation method thereof | |
| CN114149728B (en) | Impact-resistant wear-resistant polyester industrial coating 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 | |
| CN105255354A (en) | Butanone-resistant water-borne acrylic polyurethane paint and preparing method thereof | |
| Al-Zahrani et al. | Preparation and evaluation of high-performance modified alkyd resins based on 1, 3, 5-tris-(2-hydroxyethyl) cyanuric acid and study of their anticorrosive properties for surface coating applications | |
| CN107384173A (en) | A kind of hard polyurethane ester paint and preparation method thereof | |
| CN103087621A (en) | Antibacterial waterborne polyurethane wood lacquer | |
| CN104861846A (en) | Waterborne polyurethane based quick-drying wood coating with superhigh solid content | |
| Eyssa et al. | Surface characteristics of cotton/polyester fabric coated with poly-urethane elastomers cured thermally or by using gamma irradiation | |
| CN103059709B (en) | A kind of waterborne polyurethane wood coatings with antibacterial effect | |
| CN114687248B (en) | Environment-friendly decorative paper 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: 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 |