CN101857669B - Self-defoaming siloxane copolymeric isocyanate blocked prepolymer composite for spray polyurea elastomer - Google Patents
Self-defoaming siloxane copolymeric isocyanate blocked prepolymer composite for spray polyurea elastomer Download PDFInfo
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- CN101857669B CN101857669B CN 201010191392 CN201010191392A CN101857669B CN 101857669 B CN101857669 B CN 101857669B CN 201010191392 CN201010191392 CN 201010191392 CN 201010191392 A CN201010191392 A CN 201010191392A CN 101857669 B CN101857669 B CN 101857669B
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Abstract
The invention relates to a paint technology, in particular to a self-defoaming siloxane copolymeric isocyano blocked prepolymer composite which comprises the following three components: a first component, i.e. isocyanate composite providing isocyanos, a second component, i.e. a composite of hydroxyl-terminated polyether polyol and polyester polyol, and a third component, i.e. hydroxyl-terminated or/and amine-terminated siloxane composite, and can solve the problem that the interface adhesive attraction between a material and a base material is reduced, and even worse, the material can fall off because molecular heat movement leads defoamer micromolecules to shift.
Description
Technical field
The present invention relates to coating technology, relate in particular to a kind of siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming.
Background technology
Since Huntsman company took the lead in researching and developing successful spray Polyurea Elastomer Technology, the polyurea elastomer waterproof paint was solvent-free with regard to relying on, fast setting, the insensitive and excellent physical and chemical performance of humiture has been obtained swift and violent development.Particularly in recent years since, at home successful application in Beijing-Tianjin high ferro, the Beijing-Shanghai express railway, this material has become direction and the forward position of the waterproof paint development coming years, and can expect its high market share that will occupy in the field of business.
So-called Spray Polyurea Elastomer adopts Airless spraying equipment, exactly with reactant isocyano (NCO) composition of blocked prepolymer and amino (NH
2) compound of polyethers is after Quick uniform disperses in mixing section, the polyurea elastomer macromolecular material of spray mo(u)lding.But because-NCO and-NH
2The speed of reaction that generates the urea key is exceedingly fast, material viscosity sharply becomes large in the mixing section, single by regulating spraying parameter (such as product pump pressure, temperature of charge and transport pipe temperature) can't discharge the bubble that liquidates and introduce when mixing, cause the defective of material after the moulding, greatly lower the physicochemical property of material.Therefore, need in material, to add the froth breaking component in advance.
Common defoamer mainly is mineral oils, silicone oil and polyether-modified silicone oil product on the market now, this defoamer such as direct use are in Spray Polyurea Elastomer, although can effectively discharge the bubble that is involved in when mixing, but because the defoamer small molecules that molecular thermalmotion causes migration, can reduce greatly material with the Interface Adhesion effect between base material, even severe patient causes coming off of material.
Summary of the invention
In order to overcome defects, the technical problem to be solved in the present invention provides the siloxane copolymeric isocyanate blocked prepolymer composite that a kind of Spray Polyurea Elastomer is used self-defoaming.
In order to overcome the defective that exists in the background technology, the technical solution adopted for the present invention to solve the technical problems is: a kind of Spray Polyurea Elastomer siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming, it is characterized in that: have three kinds of components, the first component is for providing the isocyanate composition of isocyano, second component is to contain the polyether glycol of terminal hydroxy group and the composition of polyester polyol, and the 3rd component is that terminal hydroxy group is or/and the amino silicone composition of end.
The content of the isocyanic ester described in the present invention accounts for the 15wt% of prepolymer.
In prepolymer, its content is 0.5～2.0wt% to siloxanes described in the present invention with the covalent bond structure copolymerization.
Isocyanic ester described in the present invention is 2,4 '-diphenylmethanediisocyanate and 4, the mixture of 4 ' diphenylmethanediisocyanate.
Isocyanic ester described in the present invention is 2,4 '-diphenylmethanediisocyanate and 4, and the content ratio of the mixture of 4 ' diphenylmethanediisocyanate is 1: 1.
End hydroxy polyether polyvalent alcohol described in the present invention is one or both mixture of polyglycol ether, PTMG.
The molecular-weight average of the end hydroxy polyether polyvalent alcohol described in the present invention is 400～3000.
The polyvalent alcohol of hydroxyl telechelic polyester described in the present invention is that average molecular weight forms in diprotic acid and the polyvalent alcohol mass polymerization of 400-3000.Wherein diprotic acid is one or more combination thing in m-phthalic acid, terephthalic acid, hexanodioic acid, the sebacic acid, and polyvalent alcohol is the one or more combination thing in ethylene glycol, glycol ether, the butyleneglycol.
Terminal hydroxy group of the present invention is or/and the amino silicone composition of end is that number-average molecular weight is at the silicone oil composite of 400-2000.
Particularly the preparation method of described self-defoaming copolymeric siloxane-NCO blocked prepolymer composite is: under nitrogen protection; isocyanic ester is joined in the dry reactor; add again polyether glycol and polyester polyol under the condition of stirring at room; add terminal hydroxy group at last or/and the amino siloxanes of end; stir and half an hour raw material is evenly mixed; be warming up to again 40-60 ℃ of reaction 2-3 hour, be warming up at last 70-90 ℃ of reaction 2-3 hour, until reaction finishes.
When the present invention uses with its with the compound of amino-polyether take volume ratio as 1: 1 ,-NCO and-NH
2Mol ratio be 1.1: 1, adopt the moulding of Airless spraying equipment.The spray polyurea processing parameter is 80 ℃ of copolymeric siloxanes-NCO blocked prepolymer composite temperature of charge, pump pressure 2000mPa; 70 ℃ of the compound temperature of charge of amino-polyether, pump pressure 2000mPa; 80 ℃ of transfer lime temperature.
Beneficial effect: the present invention passes through Molecular Structure Design, select the terminal hydroxy group with reactive behavior or/and aminosiloxane, copolymerization is in the prepolymer composite of-NCO root end-blocking, realized the self-defoaming in the spray polyurea process, and since siloxane structure with the copolymerization of covalent linkage form in the molecular chain of material, effectively reduce its transporting action, guarantee that material is with high-intensity bonding between base material.
Embodiment
Embodiment one
Under nitrogen protection; the liquefied mdi of 50.8kg is joined in the dry reactor; the molecular weight that adds 48.2kg under the stirring at room condition is 2000 polyglycol ethers; the molecular weight that adds at last 1kg is 2000 terminal hydroxy group siloxanes; stir and half an hour raw material is evenly mixed; be warming up to again 50 ℃ of reactions 3 hours, be warming up at last 80 ℃ of reactions 3 hours, obtain the siloxane copolymeric isocyanate blocked prepolymer composite 1 of self-defoaming.
Embodiment two
Under nitrogen protection; the liquefied mdi of 55.7kg is joined in the dry reactor; the molecular weight that adds 43.3kg under the stirring at room condition is 1000 polyglycol ethers; the molecular weight that adds at last 1kg is 1000 terminal hydroxy group siloxanes; stir and half an hour raw material is evenly mixed; be warming up to again 50 ℃ of reactions 2 hours, be warming up at last 80 ℃ of reactions 2 hours, obtain the siloxane copolymeric isocyanate blocked prepolymer composite 2 of self-defoaming.
Embodiment three
Under nitrogen protection; the liquefied mdi of 53.4kg is joined in the dry reactor; the molecular weight that adds 22.8kg under the stirring at room condition is 2000 polyglycol ethers; the molecular weight that adds again 22.8kg is 1000 polyglycol ethers; the molecular weight that adds at last 1kg is 2000 terminal hydroxy group siloxanes, stirs half an hour raw material evenly to be mixed, and is warming up to 50 ℃ of reactions 3 hours again; be warming up at last 80 ℃ of reactions 3 hours, obtain the siloxane copolymeric isocyanate blocked prepolymer composite 3 of self-defoaming.
Embodiment four
Under nitrogen protection; the liquefied mdi of 56.6kg is joined in the dry reactor; the molecular weight that adds 29.6kg under the stirring at room condition is 2000 polyglycol ethers; the molecular weight that adds again 13.0kg is 400 polyglycol ethers; the molecular weight that adds at last 0.8kg is 2000 terminal hydroxy group siloxanes, stirs half an hour raw material evenly to be mixed, and is warming up to 50 ℃ of reactions 2 hours again; be warming up at last 80 ℃ of reactions 2 hours, obtain the siloxane copolymeric isocyanate blocked prepolymer composite 4 of self-defoaming.
Embodiment five
Under nitrogen protection; the liquefied mdi of 50.8kg is joined in the dry reactor; adding 23.6kg molecular weight is 2000 polyglycol ether under the stirring at room condition; add again the 23.6kg molecular weight and be 2000 polyester diol; the molecular weight that adds at last 2kg is 2000 terminal hydroxy group siloxanes; stirring evenly mixes raw material half an hour, is warming up to 50 ℃ of reactions 3 hours again, is warming up at last 80 ℃ of reactions 2 hours.Wherein polyester diol is the 26.6kg sebacic acid, the 6.4kg hexanodioic acid, and the 14.5kg terephthalic acid, the 14.5kg m-phthalic acid, 32.5kg sweet two pure and mild 5.5kg ethylene glycol mass polymerizations form, and obtain the siloxane copolymeric isocyanate blocked prepolymer composite 5 of self-defoaming.
Table one: with above five groups of polyurea elastomer materials that embodiment was produced
| Tensile strength/mPa | Elongation at break/% | Pull strength/mPa | Pore | |
| Embodiment 1 | 25.6 | 628 | 5.2 | Nothing |
| Embodiment 2 | 29.2 | 486 | 6.1 | Nothing |
| Embodiment 3 | 28.7 | 542 | 5.6 | Nothing |
| Embodiment 4 | 28.9 | 493 | 5.8 | Nothing |
| Embodiment 5 | 30.2 | 537 | 6.5 | Nothing |
Claims (7)
1. a Spray Polyurea Elastomer is with the siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming, it is characterized in that: have three kinds of components, the first component is for providing the isocyanate composition of isocyano, second component is to contain the polyether glycol of terminal hydroxy group and the composition of polyester polyol, the 3rd component is terminal hydroxy group or/and the amino silicone composition of end, wherein siloxane structure with the covalent bond structure copolymerization in the molecular chain structure of isocyano blocked prepolymer; And its reaction process is: under nitrogen protection; isocyanic ester is joined in the dry reactor; add again polyether glycol and the polyester polyol that contains terminal hydroxy group under the condition of stirring at room; add terminal hydroxy group at last or/and the end aminosiloxane; stir and half an hour raw material is evenly mixed; be warming up to again 40-60 ℃ of reaction 2-3 hour, be warming up at last 70-90 ℃ of reaction 2-3 hour, until reaction finishes.
2. Spray Polyurea Elastomer as claimed in claim 1 is with the siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming, and it is characterized in that: the content of described isocyanic ester accounts for the 15wt% of prepolymer.
3. Spray Polyurea Elastomer as claimed in claim 1 is with the siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming, and it is characterized in that: in prepolymer, its content is 0.5～2.0wt% to described siloxanes with the covalent bond structure copolymerization.
4. Spray Polyurea Elastomer as claimed in claim 1 is with the siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming, it is characterized in that: described isocyanic ester is 2,4 '-diphenylmethanediisocyanate and 4, the mixture of 4 '-diphenylmethanediisocyanate.
5. Spray Polyurea Elastomer as claimed in claim 4 is with the siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming, it is characterized in that: described isocyanic ester is 2,4 '-diphenylmethanediisocyanate and 4, the mixture of 4 '-diphenylmethanediisocyanate, wherein, 2,4 '-diphenylmethanediisocyanate and 4, the content ratio of 4 '-diphenylmethanediisocyanate is 1: 1.
6. Spray Polyurea Elastomer as claimed in claim 1 is characterized in that: the mixture of one or both that described end hydroxy polyether polyvalent alcohol is polyglycol ether, PTMG with the siloxane copolymeric isocyanate blocked prepolymer composite of self-defoaming.
7. such as the siloxane copolymeric isocyanate blocked prepolymer composite of claim 1 or 6 described Spray Polyurea Elastomers usefulness self-defoamings, it is characterized in that: the molecular-weight average of described end hydroxy polyether polyvalent alcohol is 400～3000.
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| CN 201010191392 CN101857669B (en) | 2010-06-04 | 2010-06-04 | Self-defoaming siloxane copolymeric isocyanate blocked prepolymer composite for spray polyurea elastomer |
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| CN 201010191392 CN101857669B (en) | 2010-06-04 | 2010-06-04 | Self-defoaming siloxane copolymeric isocyanate blocked prepolymer composite for spray polyurea elastomer |
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| CN101857669B true CN101857669B (en) | 2013-02-13 |
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| CN103468110B (en) * | 2013-09-23 | 2016-01-27 | 句容市石狮冲压件厂 | A kind of waterproof paint |
| DE102018114549A1 (en) * | 2018-06-18 | 2019-12-19 | CHT Germany GmbH | Polyurethane organopolysiloxanes with carbodiimide groups |
| CN113980563B (en) * | 2021-12-24 | 2022-03-29 | 科顺防水科技股份有限公司 | Method for preparing one-component semi-polyurea waterproof coating composition and one-component semi-polyurea waterproof coating composition |
| CN114479628B (en) * | 2021-12-24 | 2023-03-17 | 佛山市南海起弘新材料科技有限公司 | Polyurethane coating for shoes and preparation method of coating thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368062A (en) * | 2008-10-10 | 2009-02-18 | 海洋化工研究院 | High-temperature resistant water spray coating polyurea flexible composition, preparation, construction method and uses thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368062A (en) * | 2008-10-10 | 2009-02-18 | 海洋化工研究院 | High-temperature resistant water spray coating polyurea flexible composition, preparation, construction method and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘培礼等."喷涂聚脲弹性体改性的研究进展".《聚氨酯工业》.2008,第23卷(第5期),第5-8页. |
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Denomination of invention: Self defoaming siloxane copolymerized isocyanate terminated prepolymer composition for spraying polyurea elastomer Effective date of registration: 20210928 Granted publication date: 20130213 Pledgee: Industrial and Commercial Bank of China Limited Changzhou Economic Development Zone sub branch Pledgor: JIANGSU LANLING POLYMER MATERIAL Co.,Ltd. Registration number: Y2021980010096 |
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