CN107011787B - Solvent-free polyurethane with long operation time and preparation method thereof - Google Patents
Solvent-free polyurethane with long operation time and preparation method thereof Download PDFInfo
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- CN107011787B CN107011787B CN201611162446.XA CN201611162446A CN107011787B CN 107011787 B CN107011787 B CN 107011787B CN 201611162446 A CN201611162446 A CN 201611162446A CN 107011787 B CN107011787 B CN 107011787B
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- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- 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
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses solvent-free polyurethane with long operation time and a preparation method thereof. The polyester resin is a copolymer of castor oil, phthalic anhydride and trihydroxypropane. The special polyether resin is as follows: alkylene oxide based mosaic copolymers based on trimethylolpropane TMP as initiator, said alkylene oxides comprising propylene oxide, ethylene oxide and mixtures thereof. The improved solvent-free polyurethane can obviously prolong the gel operation time of the solvent-free polyurethane terrace material, is closer to the epoxy gel time, greatly reduces the construction difficulty and reduces the risk of terrace engineering.
Description
Technical Field
The invention relates to the technical field of paint, in particular to solvent-free polyurethane with long operation time and a preparation method thereof.
Background
The paint has good anti-corrosion effect as a protective layer, and has the advantages of simple construction, strong adaptability, easy maintenance, good economic benefit and the like, thereby being widely applied to the field of pipeline anti-corrosion. Among them, solvent-free polyurethane paint is used as an environment-friendly high-performance paint, which causes more and more attention in pipeline protection.
The solvent-free polyurethane paint is mainly formed by gradual addition polymerization reaction of binary or polybasic isocyanate and binary or polybasic alcohol to form carbamate resin, and the solvent-free polyurethane macromolecule contains a large amount of polar bonds such as ester bonds, ether bonds, urea bonds, biuret bonds, allophanate bonds and the like besides polyurethane ester bonds, so that hydrogen bonds are easily formed among molecular chains, and a plurality of excellent characteristics are endowed to the solvent-free polyurethane. However, the existing solvent-free polyurethane coating still has a plurality of problems when in use, such as too short gel time and far lower than epoxy gel time, so that the available operation time is also very short, the construction difficulty is greatly increased, and the risk of terrace engineering is also increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides solvent-free polyurethane which can prolong the gel time and has long operation time and a preparation method thereof.
In order to achieve the purpose of the invention, the technical scheme is as follows:
a solvent-free polyurethane having a long pot life, comprising an a component and a B component, the a component comprising, in weight percent:
the component B is modified polymeric MDI;
wherein the proportion of the component A to the component B is 100: 80-100: 90.
preferably, the polyester resin is a copolymer of castor oil, phthalic anhydride and trimethylolpropane.
Preferably, the special polyether resin is: alkylene oxide based mosaic copolymers based on trimethylolpropane TMP as initiator, said alkylene oxides comprising propylene oxide, ethylene oxide and mixtures thereof.
Preferably, the molecular weight of the special polyether resin is 200-410, the hydroxyl value is 210-410, the metal ion content is less than 5PPM, and the water content is less than one thousandth.
Preferably, the water absorbing agent is a molecular sieve, the pH value is neutral, the pore diameter is type 4A, and the general formula is: MO.Al2O3.xSiO2.yH2O, wherein M represents K, ca, namely potassium calcium salt.
Preferably, the filler is any one or more of quartz powder, kaolin and barium sulfate.
Preferably, the defoamer I is a dispersion of silicone modified silica; the defoaming agent II is an acrylic defoaming agent; the leveling agent is an acrylic ester leveling agent; the color paste is uniform and stable color paste which is obtained by high-speed dispersion grinding and is based on polyester resin, polyurethane dispersing agent and toner; the reactive diluent is dicyclooxazolidine, propylene carbonate and ethylene glycol diacetate reactant.
Preferably, the modified polymeric MDI has a low reactivity, a viscosity of 50 to 300mpa.s and an nco content of 31.0% by modification.
A process for the preparation of a solvent-free polyurethane having a long operating time, comprising the steps of:
1.1 Preparing a molecular sieve dispersion:
according to the whole package amount of the 4A molecular sieve, putting the mixture into special polyether resin, sealing and dispersing at high speed, and sealing and preserving for standby after the fineness of the mixture is tested to be less than 20 microns;
1.2 Preparing a component A):
(1) Putting polyester resin, special polyether resin, water absorbent, filler, defoamer I, defoamer II, flatting agent and molecular sieve dispersion into a production kettle, and stirring uniformly at high speed;
(2) Different color pastes are put into according to the formulated colors, and the related quality requirements are met;
(3) Adding said reactive diluent
(4) Sealing and packaging after qualified product management;
1.3 Preparing a component B:
and directly sub-packaging the qualified vat raw materials.
And mixing the component A and the component B, uniformly stirring, and curing to obtain the solvent-free polyurethane.
The invention has the beneficial effects that:
the method has the advantages that polyether resin with lower activity is selected, a proper water scavenger (molecular sieve/zeolite powder) is selected, a proper curing agent with low activity is selected, and a retarder with a curing delaying effect is selected, so that the gel operation time of the solvent-free polyurethane terrace material is obviously prolonged, the gel time is more similar to the epoxy gel time, the construction difficulty is greatly reduced, and the risk of terrace engineering is reduced.
Detailed Description
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1
A solvent-free polyurethane having a long pot life comprising an a-component and a B-component, the a-component comprising, in weight percent:
the component B is modified polymeric MDI.
The ratio of the component A to the component B is 100:80.
The modified polymeric MDI has lower reactivity, viscosity of 50-70 mpa.s, NCO content of 31.0%, and is especially Hensman Suprasec3251 by modification.
The defoamer I is the court 6800, the court Gao Xiaopao agent N and the HX2085 of China, and the defoamer I in the embodiment is the court 6800. The second antifoaming agent is AC300 from co-mingling, taend 490, 410, etc., and in this example, the second antifoaming agent is AC300 from co-mingling. The leveling agent is an acrylate leveling agent, such as BYK35N, tagn 310, 298, etc., and in this embodiment, the leveling agent is BYK35N. The filler is quartz powder, the water absorbent is a molecular sieve, the pH value is neutral, the pore diameter is 4A type, and the general formula is: MO.Al2O3.xSiO2.yH2O, wherein M represents K, ca, namely potassium calcium salt.
The molecular weight of the special polyether resin is 200, the hydroxyl value is 220, the metal ion content is less than 5PPM, and the water content is less than one thousandth.
Example 2
A solvent-free polyurethane having a long pot life comprising an a-component and a B-component, the a-component comprising, in weight percent:
the component B is modified polymeric MDI.
The ratio of the component A to the component B is 100:89.
The modified polymeric MDI has lower reactivity, viscosity of 250-300 mpa.s, NCO content of 31.0%, and is especially Hensman Suprasec3251 by modification.
The defoamer I is a pretty 6800, a Di Gao Xiaopao agent N and a HX2085 of China, and the defoamer I in the embodiment is the HX2085 of China. The second antifoaming agent is AC300 from co-Rong, tagn 490, 410, etc., and in this example, the second antifoaming agent is Tagn 490. The leveling agent is an acrylate leveling agent, such as BYK35N, tages 310 and 298, and in this embodiment, the leveling agent is tages 310. The filler is barium sulfate, the water absorbent is a molecular sieve, the pH value is neutral, the pore diameter is 4A type, and the general formula is: MO.Al2O3.xSiO2.yH2O, wherein M represents K, ca, namely potassium calcium salt.
The molecular weight of the special polyether resin is 400, the hydroxyl value is 400, the metal ion content is less than 5PPM, and the water content is less than one thousandth.
Example 3
A solvent-free polyurethane having a long pot life comprising an a-component and a B-component, the a-component comprising, in weight percent:
the component B is modified polymeric MDI.
The ratio of the component A to the component B is 100:87.
The modified polymeric MDI has lower reactivity, viscosity of 100-200 mpa.s, NCO content of 31.0%, and is specifically Hunsman Suprasec3251 by modification.
The defoamer I is a pretty 6800, a Di Gao Xiaopao agent N and a HX2085 of China, and the defoamer I in the embodiment is the HX2085 of China. The second antifoaming agent is AC300 from co-Rong, tagn 490, 410, etc., and in this example, the second antifoaming agent is Tagn 490. The leveling agent is an acrylate leveling agent, such as BYK35N, tages 310 and 298, and in this embodiment, the leveling agent is tages 310. The filler is a mixture of quartz powder, kaolin and barium sulfate, the water absorbent is a molecular sieve, the pH value is neutral, the pore diameter is of the type 4A, and the general formula is: MO.Al2O3.xSiO2.yH2O, wherein M represents K, ca, namely potassium calcium salt.
The molecular weight of the special polyether resin is 300, the hydroxyl value is 300, the metal ion content is less than 5PPM, and the water content is less than one thousandth.
Example 4
A solvent-free polyurethane having a long pot life comprising an a-component and a B-component, the a-component comprising, in weight percent:
the component B is modified polymeric MDI.
The ratio of the component A to the component B is 100:85.
The modified polymeric MDI has lower reactivity, viscosity of 150-250 mpa.s, NCO content of 31.0%, and is especially Hensman Suprasec3251 by modification.
The defoamer I is a pretty 6800, a Di Gao Xiaopao agent N and a HX2085 of China, and the defoamer I in the embodiment is the HX2085 of China. The second antifoaming agent is AC300 from co-Rong, tagn 490, 410, etc., and in this example, the second antifoaming agent is Tagn 490. The leveling agent is an acrylate leveling agent, such as BYK35N, tages 310 and 298, and in this embodiment, the leveling agent is tages 310. The filler is a mixture of quartz powder, kaolin and barium sulfate, the water absorbent is a molecular sieve, the pH value is neutral, the pore diameter is of the type 4A, and the general formula is: MO.Al2O3.xSiO2.yH2O, wherein M represents K, ca, namely potassium calcium salt.
The molecular weight of the special polyether resin is 300, the hydroxyl value is 300, the metal ion content is less than 5PPM, and the water content is less than one thousandth.
The modified solventless polyurethane prepared in the above examples of the present invention was tested and compared with conventional solventless polyurethane, and gel times were measured at 30, 25 and 15 ℃ respectively, the average value of the measurements being shown as red, and the comparison results being shown in table 1 below:
table 1 gel time comparative test
As can be seen from the data measured in Table 1, compared with the conventional solvent-free polyurethane, the improved solvent-free polyurethane prepared by the invention greatly prolongs the gel operation time, is closer to the epoxy gel time, greatly reduces the construction difficulty and reduces the risk of terrace engineering.
Finally, it should be noted that: the above embodiments are only for illustrating the present invention and not for limiting the technical solutions described in the present invention, and therefore, although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the present invention may be modified or substituted by equivalent ones without departing from the spirit and scope of the present invention and all modifications thereof are intended to be covered in the scope of the claims of the present invention.
Claims (7)
1. A solvent-free polyurethane having a long pot life comprising an a-component and a B-component, the a-component comprising, in weight percent:
25.0-45.5% of polyester resin
8.0-15.5% of special polyether resin
0.3-1.5% of defoaming agent
0.3-0.5% of defoaming agent II,
it is characterized in that the method comprises the steps of,
wherein the proportion of the component A to the component B is 100: 80-100: 90;
the component B is modified polymeric MDI; the modified polymeric MDI has a viscosity of 50-300 mpa.s, an NCO content of 31.0% and a Hunsman Suprasec3251,
the A component also comprises:
0.3 to 0.5 percent of leveling agent
3-5% of color paste
3-5% of a reactive diluent;
8.0-15.5% of water absorbent
30-45% of filler,
the special polyether resin is as follows: alkylene oxide-based mosaic copolymers based on trimethylolpropane TMP as initiator, said alkylene oxides comprising propylene oxide, ethylene oxide and mixtures thereof,
the defoaming agent I is a dispersion liquid of organosilicon modified silicon dioxide; and the defoaming agent II is an acrylic defoaming agent.
2. The solvent-free polyurethane having a long pot life of claim 1 wherein the polyester resin is a copolymer of castor oil, phthalic anhydride and trimethylolpropane.
3. The solvent-free polyurethane having a long operating time according to claim 2, wherein the specific polyether resin has a molecular weight of 200 to 410, a hydroxyl value of 210 to 410, a metal ion content of less than 5PPM, and a water content of less than one thousandth.
4. The solvent-free polyurethane having a long operation time according to claim 1, wherein the water absorbing agent is a molecular sieve, the acid-base number is neutral, the pore size is type 4A, and the general formula is: mo. al2o3.xsio2.yh2o, wherein M represents K, ca.
5. The solvent-free polyurethane with long operation time according to claim 1, wherein the filler is any one or more of quartz powder, kaolin, and barium sulfate.
6. The solvent-free polyurethane with long run time of claim 1, wherein the leveling agent is an acrylate leveling agent; the color paste is uniform and stable color paste which is obtained by high-speed dispersion grinding based on polyester resin, polyurethane dispersing agent and toner; the reactive diluent is the reactant of dicyclooxazolidine, propylene carbonate and ethylene glycol diacetate.
7. A process for the preparation of a solvent-free polyurethane having a long run time, to produce a solvent-free polyurethane having a long run time as claimed in any one of claims 1 to 6, comprising the steps of:
1.1 Preparing a molecular sieve dispersion:
according to the whole package amount of the 4A molecular sieve, putting the mixture into special polyether resin, sealing and dispersing at high speed, and sealing and preserving for standby after the fineness of the mixture is tested to be less than 20 microns;
1.2 Preparing a component A):
(1) Putting polyester resin, special polyether resin, water absorbent, filler, defoamer I, defoamer II, flatting agent and molecular sieve dispersion into a production kettle, and stirring uniformly at high speed;
(2) Different color pastes are put into according to the formulated colors, and the related quality requirements are met;
(3) Adding said reactive diluent
(4) Sealing and packaging after qualified product management;
1.3 Preparing a component B:
directly sub-packaging the qualified vat raw materials;
and mixing the component A and the component B, uniformly stirring, and curing to obtain the solvent-free polyurethane.
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| CN110183607B (en) * | 2019-06-04 | 2022-01-14 | 北京东方雨虹防水技术股份有限公司 | Double-component water plugging reinforcing grouting material and preparation method thereof |
| CN112456938B (en) * | 2020-12-10 | 2022-08-26 | 上海阳森精细化工有限公司 | High-fluidity long-operation-period polyurethane urea cement concrete mortar terrace |
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