CN104311785A - Preparation method of flame-retardant type self-crosslinked spraying polyurea elastic emulsion - Google Patents
Preparation method of flame-retardant type self-crosslinked spraying polyurea elastic emulsion Download PDFInfo
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- CN104311785A CN104311785A CN201410491480.6A CN201410491480A CN104311785A CN 104311785 A CN104311785 A CN 104311785A CN 201410491480 A CN201410491480 A CN 201410491480A CN 104311785 A CN104311785 A CN 104311785A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
- C09D175/02—Polyureas
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
A preparation method of a flame-retardant type self-crosslinked spraying polyurea elastic emulsion comprises the steps: taking IPDI, GE-220A, D-2000 and DMPA as raw materials for preparation of a prepolymer, adding a proper amount of silica sol, modifying the prepolymer, adding DHPA, carrying out crosslinking chain extension, adding triethylamine, carrying out a neutralization reaction to form a salt, and adding an N-ethyl-3,6-diamine carbazole aqueous solution to prepare the halogen-free flame-retardant silica sol modified waterborne polyurethane emulsion. The obtained flame-retardant type self-crosslinked spraying polyurea elastic emulsion after filming has relatively good thermal stability, hardness and flame retardant performance.
Description
Technical field
The present invention relates to a kind of preparation method of flame retardant type self-crosslinking spray polyurea elastomer emulsion, belong to chemical field.
technical background
Spray polyurea elastic material is the protective coating that a kind of pollution-free, high-performance, fast setting, solid content that recent two decades grows up reach more than 95%, this coating can inside, spraying application on the various structures such as curved surface, simultaneously, due to fast setting, make polyurea elastomer insensitive to moisture, moisture, temperature etc., due to the curing characteristics that it is good, polyureas has been widely used in waterproof, the inefficient field of traditional material such as anticorrosion.
Silicon-series five-retardant causes the attention of common people because hazardous property is low, can be divided into inorganic silicon and organic silicon fibre retardant by composition structure.The former is mainly silicon-dioxide, has reinforcement and fire retardation concurrently.Organic silicon fibre retardant mainly contains silicone oil, silicone resin, silicon rubber and organosilane alcohol amide etc.Silicon sol is the colloidal solution that the colloidal particle of silicon-dioxide are scattered in white in water or blue micro-band blue-opalescent, has another name called silicic acid sol, or silica hydrosol.It presents unreactiveness, odorless, tasteless, nontoxic, corrosion-free.
Summary of the invention
The object of this invention is to provide a kind of preparation method of flame retardant type self-crosslinking spray polyurea elastomer emulsion, there is good thermostability, hardness and flame retardant properties.
For realizing above object, the preparation method of a kind of flame retardant type self-crosslinking spray polyurea elastomer emulsion of the present invention, its preparation method is specially:
(1) performed polymer is prepared with isophorone diisocyanate (IPDI), end hydroxy polyether (GE-220A), Amino Terminated polyether(ATPE) (D-2000), dimethylol propionic acid (DMPA) for raw material, reaction 2h;
(2) add silica sol modified performed polymer, silicon sol accounts for 15% of performed polymer quality, reaction 50min; Add 3-[two-(2-hydroxyethyl)] amido-N (1,1-dimethyl-3 butanone) propionic acid amide (DHPA) and be cross-linked chain extension to performed polymer, the consumption of DHPA is 4% of performed polymer quality;
(3) be cooled to 40 DEG C, add triethylamine and carry out neutralization reaction generation salt, reaction 3-4min;
(4) at N-ethyl-3, magnesium powder is added in 6-dinitrobenzene carbazole, slowly add concentrated hydrochloric acid again, be back to yellow mercury oxide and become white precipitate, filter rear water dissolution, be in the sodium hydroxide of 10% by mass concentration and above-mentioned solution, be greater than 10 to pH, after filtering, recrystallization obtains N-ethyl-3,6-diaminocarbazole;
(5) aqueous solution of N-ethyl-3,6-diaminocarbazole is joined in the salts solution of step (3) carry out emulsification 60min, obtain flame retardant type self-crosslinking spray polyurea elastomer emulsion.
In step (1), the proportioning of performed polymer raw material is: the mol ratio of IPDI and GE-220A, D-2000, DMPA is the 2%-3% that 1.2:1-1.3:1, D-2000 account for performed polymer quality, and DMPA accounts for the 5%-6% of performed polymer quality.
In step (3), the amount of substance of triethylamine is identical with the amount of substance of DMPA.
In step (4), the mass ratio of N-ethyl-3,6-dinitrobenzene carbazole and magnesium powder is 1:2.
In step (5), the consumption of N-ethyl-3,6-diaminocarbazole is 0.1% of performed polymer quality; The consumption of water is 2 times of performed polymer total mass.
The beneficial effect that the present invention produces is, this patent adopts Nano silica sol to carry out modified polyurea elastic emulsion, Nano silica sol is joined in the mode of physical blending in the aqueous polyurethane emulsion synthesized, greatly enhance the flame retardant properties of polyurea elastic material, improve mechanical property, hardness and thermostability simultaneously, have larger Research Significance in practical application side.
Embodiment
Embodiment 1:
Prepare chainextender N-ethyl-3,6-diaminocarbazole: add magnesium powder in N-ethyl-3,6-dinitrobenzene carbazole, described N-ethyl-3, the mass ratio of 6-dinitrobenzene carbazole and magnesium powder is 1:2, slowly add concentrated hydrochloric acid again, be back to yellow mercury oxide and become white precipitate, filter rear water dissolution, be in the sodium hydroxide of 10% by mass concentration and above-mentioned solution, be greater than 10 to pH, after filtering, recrystallization obtains N-ethyl-3,6-diaminocarbazole.
Embodiment 2:
Prepare flame retardant type self-crosslinking spray polyurea elastomer emulsion: prepare performed polymer with isophorone diisocyanate (IPDI), end hydroxy polyether (GE-220A), Amino Terminated polyether(ATPE) (D-2000), dimethylol propionic acid (DMPA) for raw material, reaction 2h.The mol ratio of IPDI and GE-220A, D-2000, DMPA be 1.2:1, D-2000 account for that 2%, DMPA of performed polymer quality accounts for performed polymer quality 5%.Add silica sol modified performed polymer, silicon sol accounts for 15% of performed polymer quality, reaction 50min; Add 3-[two-(2-hydroxyethyl)] amido-N (1,1-dimethyl-3 butanone) propionic acid amide (DHPA) and be cross-linked chain extension to performed polymer, the consumption of DHPA is 4% of performed polymer quality.Be cooled to 40 DEG C, add triethylamine and carry out neutralization reaction generation salt, reaction 3min.The amount of substance of triethylamine is identical with the amount of substance of DMPA.The aqueous solution adding N-ethyl-3,6-diaminocarbazole carries out emulsification 60min, and the consumption of water is 2 times of performed polymer total mass, obtains flame retardant type self-crosslinking spray polyurea elastomer emulsion.
Through recording, the gel time of polyurea elastic material of the present invention is 134s, and tensile strength is 85.5MPa, and oxygen index is 57.2%.
Embodiment 3:
Prepare flame retardant type self-crosslinking spray polyurea elastomer emulsion: prepare performed polymer with isophorone diisocyanate (IPDI), end hydroxy polyether (GE-220A), Amino Terminated polyether(ATPE) (D-2000), dimethylol propionic acid (DMPA) for raw material, reaction 2h.The mol ratio of IPDI and GE-220A, D-2000, DMPA be 1.3:1, D-2000 account for that 3%, DMPA of performed polymer quality accounts for performed polymer quality 6%.Add silica sol modified performed polymer, silicon sol accounts for 15% of performed polymer quality, reaction 50min; Add 3-[two-(2-hydroxyethyl)] amido-N (1,1-dimethyl-3 butanone) propionic acid amide (DHPA) and be cross-linked chain extension to performed polymer, the consumption of DHPA is 4% of performed polymer quality.Be cooled to 40 DEG C, add triethylamine and carry out neutralization reaction generation salt, reaction 3min.The amount of substance of triethylamine is identical with the amount of substance of DMPA.The aqueous solution adding N-ethyl-3,6-diaminocarbazole carries out emulsification 60min, and the consumption of water is 2 times of performed polymer total mass, obtains flame retardant type self-crosslinking spray polyurea elastomer emulsion.
Through recording, the gel time of polyurea elastic material of the present invention is 122s, and tensile strength is 87.1MPa, and oxygen index is 46.5%.
Claims (6)
1. a preparation method for flame retardant type self-crosslinking spray polyurea elastomer emulsion, is characterized in that: the preparation method of this emulsion is as follows:
(1) with IPDI, GE-220A, D-2000, DMPA for performed polymer prepared by raw material, reaction 2h;
(2) add silica sol modified performed polymer, silicon sol accounts for 15% of performed polymer quality, reaction 50min; Add DHPA and be cross-linked chain extension to performed polymer, the consumption of DHPA is 4% of performed polymer quality;
(3) be cooled to 40 DEG C, add triethylamine and carry out neutralization reaction generation salts solution, reaction 3-4min;
(4) at N-ethyl-3, magnesium powder is added in 6-dinitrobenzene carbazole, slowly add concentrated hydrochloric acid again, be back to yellow mercury oxide and become white precipitate, filter rear water dissolution, be in the sodium hydroxide of 10% by mass concentration and above-mentioned solution, be greater than 10 to pH, after filtering, recrystallization obtains N-ethyl-3,6-diaminocarbazole;
(5) aqueous solution of N-ethyl-3,6-diaminocarbazole is joined in the salts solution of step (3) carry out emulsification 60min, obtain flame retardant type self-crosslinking spray polyurea elastomer emulsion.
2. the preparation method of a kind of flame retardant type self-crosslinking spray polyurea elastomer emulsion as claimed in claim 1, it is characterized in that: in described step (1), the proportioning of performed polymer raw material is: the mol ratio of IPDI and GE-220A, D-2000, DMPA is 1.2:1-1.3:1, D-2000 accounts for the 2%-3% of performed polymer quality, and DMPA accounts for the 5%-6% of performed polymer quality.
3. the preparation method of a kind of flame retardant type self-crosslinking spray polyurea elastomer emulsion as claimed in claim 1, is characterized in that: in described step (3), the amount of substance of triethylamine is identical with the amount of substance of DMPA.
4. the preparation method of a kind of spray polyurea elastic material as claimed in claim 1, is characterized in that: in described step (4), the mass ratio of N-ethyl-3,6-dinitrobenzene carbazole and magnesium powder is 1:2.
5. the preparation method of a kind of spray polyurea elastic material as claimed in claim 1, is characterized in that: in described step (5), the consumption of N-ethyl-3,6-diaminocarbazole is 0.1% of performed polymer quality.
6. the preparation method of a kind of flame retardant type self-crosslinking spray polyurea elastomer emulsion as claimed in claim 1, is characterized in that: in described step (5), the consumption of water is 2 times of performed polymer total mass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410491480.6A CN104311785A (en) | 2014-09-24 | 2014-09-24 | Preparation method of flame-retardant type self-crosslinked spraying polyurea elastic emulsion |
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| CN201410491480.6A CN104311785A (en) | 2014-09-24 | 2014-09-24 | Preparation method of flame-retardant type self-crosslinked spraying polyurea elastic emulsion |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219643A (en) * | 2017-12-29 | 2018-06-29 | 梅庆波 | A kind of preparation method of flame-retardant polyurethane synthetic leather |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012733A (en) * | 2012-12-19 | 2013-04-03 | 青岛海尔软件有限公司 | Method for preparing mono-component normal-temperature self-crosslinking water-based polyurethane |
| CN103694445A (en) * | 2013-12-12 | 2014-04-02 | 青岛海洋新材料科技有限公司 | Preparation method of spray polyurea elastic material |
| CN103739815A (en) * | 2013-12-13 | 2014-04-23 | 青岛海洋新材料科技有限公司 | Preparation method of flame-retardant spraying polyurea elastic emulsion |
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- 2014-09-24 CN CN201410491480.6A patent/CN104311785A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012733A (en) * | 2012-12-19 | 2013-04-03 | 青岛海尔软件有限公司 | Method for preparing mono-component normal-temperature self-crosslinking water-based polyurethane |
| CN103694445A (en) * | 2013-12-12 | 2014-04-02 | 青岛海洋新材料科技有限公司 | Preparation method of spray polyurea elastic material |
| CN103739815A (en) * | 2013-12-13 | 2014-04-23 | 青岛海洋新材料科技有限公司 | Preparation method of flame-retardant spraying polyurea elastic emulsion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219643A (en) * | 2017-12-29 | 2018-06-29 | 梅庆波 | A kind of preparation method of flame-retardant polyurethane synthetic leather |
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Application publication date: 20150128 |