CN105461880A - Superhigh-modulus resin used for fiber waterproof coatings and preparing method thereof - Google Patents
Superhigh-modulus resin used for fiber waterproof coatings and preparing method thereof Download PDFInfo
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- CN105461880A CN105461880A CN201510807671.3A CN201510807671A CN105461880A CN 105461880 A CN105461880 A CN 105461880A CN 201510807671 A CN201510807671 A CN 201510807671A CN 105461880 A CN105461880 A CN 105461880A
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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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/70—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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C09D175/06—Polyurethanes from polyesters
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to superhigh-modulus resin used for fiber waterproof coatings. The resin is characterized in that a raw material formula of the resin comprises 12.5-18.5% of special polyester polyol, a small-molecule polyol mixture including 1-2% of 1,4-butanediol, 1-2% of ethylene glycol and 1-1.5% of neopentyl glycol, isocyanate that is 7-14% of 4,4'-methylenediphenyl diisocyanate, an organic solvent that is 55-72% of dimethylformamide, 0.1-0.3% of an antioxidant 1010 and 0.3-0.5% of a water seepage resisting agent 0750; the resin and a preparing method thereof are provided; and the special polyester polyol is adopted to reduce the content of hard segments in resin synthesizing processes, thus providing deformation resilience, avoiding generation of white marks and improving product quality.
Description
Technical field
The present invention relates to a kind of urethane resin, fiber water-proof coating resin particularly relating to a kind of ultra high modulus and preparation method thereof.
Background technology
At present, water-proof coating resin many uses urethane resin, the many employing polyethers of this urethane resin or polyester polyol and di-isocyanate reaction, prepare the high viscosity prepolymer that end group is-NCO, add the appropriate lower boiling solvent of people (acetone, butanone or tetrahydrofuran (THF)) to reduce viscosity, then induce one hydrophilic radical chain extension, then solubilizing agent reduces viscosity, add emulsifying water under high velocity agitation, reaction terminates rear underpressure distillation except desolventizing and obtains polyaminoester emulsion.The advantage of this method is that technique is simple, and reaction is easy to control, reproducible, emulsion particle diameter scope is large, the quality of production good, is widely used in industrial production.But this resin is by soft section, hard section synthesis, wherein soft section is made up of polyester polyol, hard section is made up of small molecule polyol, diamines chain extension and diisocyanates, in this building-up process, hard segment content is many, and deformation occurs after causing resins synthesis can produce white trace, affect the quality of product.
Summary of the invention
In view of the above, fiber water-proof coating resin that the object of the present invention is to provide a kind of ultra high modulus and preparation method thereof, reduce in resin synthesis process by adopting a kind of particular polyesters polyvalent alcohol, the content of hard section, and then the recovery of its deformation is provided, avoid the generation of white trace, improve the quality of product.
A kind of fiber water-proof coating resin of ultra high modulus, it is characterized in that, its composition of raw materials comprises particular polyesters polyvalent alcohol, small molecule polyol mixture, isocyanic ester, organic solvent, antioxidant, impervious aqua, wherein, described particular polyesters polyvalent alcohol is by oxalic acid, para Toluic Acid, glycol ether is as Material synthesis, described small molecule polyol mixture comprises 1, 4-butyleneglycol, ethylene glycol, neopentyl glycol, described isocyanic ester is 4, 4-diphenylmethanediisocyanate, described organic solvent is dimethyl formamide, in the total mass of urethane resin, the mass content of above-mentioned each component is as follows:
Particular polyesters polyvalent alcohol 12.5-18.5%;
Small molecule polyol mixture: BDO 1-2%, ethylene glycol 1-2%, neopentyl glycol 1-1.5%;
Isocyanic ester: 4,4-diphenylmethanediisocyanate 7-14%;
Organic solvent: dimethyl formamide 55-72%;
Antioxidant 1010: 0.1-0.3%;
Impervious aqua 0750:0.3%-0.5%;
Wherein, in particular polyesters polyvalent alcohol for total mass, the mass content of each component of described particular polyesters polyvalent alcohol is as follows: oxalic acid 15-20%; Para Toluic Acid 30-40%, glycol ether 35-55% synthesize.
And the preparation method of this high-rebound polyurethane resin comprises the following steps:
(1) the particular polyesters polyvalent alcohol of organic solvent and the formula ratio of part, small molecule polyol mixture, antioxidant are dropped into stirring at normal temperature in reactor simultaneously and mix, wherein, churning time must not be less than 30min;
(2) put in reactor by 4,4-diphenylmethanediisocyanates of 90% amount in formula ratio several times, and temperature of reaction controls at 70-80 DEG C, the reaction times must not be less than 120min;
(3) carry out correction thickening after having reacted in (2) step, namely add 4,4-diphenylmethanediisocyanates of remaining 10% amount in formula ratio to reactor;
(4) after reactor medium viscosity reaches 100,000 CPS/25 DEG C, start sampling and testing, after sampling and testing viscosity reaches 8-12 ten thousand CPS/25 DEG C, in reactor, add the impervious aqua of remaining organic solvent and formula ratio;
(5) repetition measurement viscosity qualified stable after carry out cooling and process, temperature controls less than 60 DEG C 40 DEG C with loading and unloading material.
Preferably, the amount that the preparation method of this high-rebound polyurethane resin adds organic solvent in (1) step is 40% of formula ratio, and the amount adding organic solvent in (4) step is 60% of formula ratio, and churning time controls at 45min in (1) step.
Preferably, the preparation method of this high-rebound polyurethane resin in (2) step by formula ratio 90% 4,4-diphenylmethanediisocyanate divides equally three times, and every minor tick 30min drops in reactor, and in (2) step the reaction times control at 180min.
Preferential and beneficial effect of the present invention is:
1. in formula, pass through particular polyesters polyvalent alcohol, this polyester polyol is by oxalic acid 15-20%; Para Toluic Acid 30-40%, glycol ether 35-55% synthesize, and this polyester polyol can reduce the content of hard section effectively, and then improves the proportion shared by soft section accordingly, thus improves its recovery of shape.
2. in formula particular polyesters polyvalent alcohol by oxalic acid, para Toluic Acid, glycol ether as Material synthesis, phenyl ring introduced by polyurethane molecular chain, improves mechanical property and the shape-memory properties of urethane.And make the structure of hard section on polyurethane molecular chain more stable.
3. in whole production process, adding in isocyanic ester process, aliquot interval is adopted to add, isocyanic ester and polyester polyol is made to react more abundant, simultaneously, after isocyanic ester and polyester polyol initial reaction complete at that time, again add isocyanic ester and carry out correction thickening, accelerate the viscosity of reaction material.
4. the preparation method of urethane resin of the present invention is simple to operate, does not need a large amount of auxiliary agents, does not need the isolation andpurification of high complexity, reduce the content of hard section by polyester polyol performance in feed change, improve its recovery of shape performance.。
Embodiment
In conjunction with following specific embodiment, the present invention will be further described in detail, but the invention is not restricted to these implements.
Embodiment 1
A kind of fiber water-proof coating resin of ultra high modulus, formed by the preparation of raw material of lower routine mass parts (kg): particular polyesters polyvalent alcohol 12.5,1,4-butyleneglycol 1.2, ethylene glycol 1.2, neopentyl glycol 1.2,4,4-diphenylmethanediisocyanate 9, dimethyl formamide 62, antioxidant (1010) 0.15, impervious aqua (0750) 0.39.
Preparation method first synthesizes special polyester polyol, due to oxalic acid 2.2; Para Toluic Acid 3.9, glycol ether 6.8 add in reactor, be heated to 155 DEG C and start to distill, and degree of intensification is to 210 DEG C.
By dimethyl formamide 24.8, particular polyesters polyvalent alcohol 12.5, 1, 4-butyleneglycol 1.2, ethylene glycol 1.2, neopentyl glycol 1.2, antioxidant (1010) 0.15 drops into stirring at normal temperature in reactor, and rotating speed is 230 revs/min, churning time is 45min, then just 4 are added at interval of 30min, 4-diphenylmethanediisocyanate 2.7, add altogether 3 times, temperature of reaction control 70-80 DEG C, reaction times is 180min, again add 4, 4-diphenylmethanediisocyanate 0.9, sampling and testing is started after reactor medium viscosity reaches 100,000 CPS/25 DEG C, after sampling and testing viscosity reaches 8-12 ten thousand CPS/25 DEG C, dimethyl formamide is added: 37.2 in reactor, with impervious aqua (0750) 0.39.Repetition measurement viscosity qualified stable after carry out cooling and process, temperature controls less than 60 DEG C 40 DEG C with loading and unloading material.
Table 1 is the fiber water-proof coating resin property detected result of ultra high modulus in embodiment 1
Embodiment 2
A kind of fiber water-proof coating resin of ultra high modulus, formed by the preparation of raw material of lower routine mass parts (kg): particular polyesters polyvalent alcohol 18.5,1,4-butyleneglycol 1.9, ethylene glycol 1.9, neopentyl glycol 1.5,4,4-diphenylmethanediisocyanate 14, dimethyl formamide 72, antioxidant (1010) 0.3, impervious aqua (0750) 0.48.
Preparation method is the synthesis using the method for synthesizing special polyester polyol in embodiment 1 first to carry out special polyurethane polyol,
By dimethyl formamide 28.8, particular polyesters polyvalent alcohol 18.5, 1, 4-butyleneglycol 1.9, ethylene glycol 1.9, neopentyl glycol 1.5, antioxidant (1010) 0.3 drops into stirring at normal temperature in reactor, and rotating speed is 250 revs/min, churning time is 45min, then just 4 are added at interval of 30min, 4-diphenylmethanediisocyanate 4.2, add altogether 3 times, temperature of reaction control 70-80 DEG C, reaction times is 180min, again add 4, 4-diphenylmethanediisocyanate 1.4, sampling and testing is started after reactor medium viscosity reaches 100,000 CPS/25 DEG C, after sampling and testing viscosity reaches 8-12 ten thousand CPS/25 DEG C, dimethyl formamide is added: 43.2 in reactor, with impervious aqua (0750) 0.48.Repetition measurement viscosity qualified stable after carry out cooling and process, temperature controls less than 60 DEG C 40 DEG C with loading and unloading material.
Table 2 is the fiber water-proof coating resin property detected result of ultra high modulus in embodiment 1
Last it is noted that the foregoing is only the preferred embodiments of the present invention; be not limited to the present invention; although with reference to previous embodiment to invention has been detailed description; for a person skilled in the art; it still can be modified to the technical scheme described in foregoing embodiments; or equivalent replacement is carried out to wherein portion of techniques feature; within the spirit and principles in the present invention all; any amendment of doing, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. the fiber water-proof coating resin of a ultra high modulus, it is characterized in that, its composition of raw materials comprises particular polyesters polyvalent alcohol, small molecule polyol mixture, isocyanic ester, organic solvent, antioxidant, impervious aqua, wherein, described particular polyesters polyvalent alcohol is by oxalic acid, para Toluic Acid, glycol ether is as Material synthesis, described small molecule polyol mixture comprises 1, 4-butyleneglycol, ethylene glycol, neopentyl glycol, described isocyanic ester is 4, 4-diphenylmethanediisocyanate, described organic solvent is dimethyl formamide, in the total mass of urethane resin, the mass content of above-mentioned each component is as follows:
Particular polyesters polyvalent alcohol 12.5-18.5%;
Small molecule polyol mixture: BDO 1-2%, ethylene glycol 1-2%, neopentyl glycol 1-1.5%;
Isocyanic ester: 4,4-diphenylmethanediisocyanate 7-14%;
Organic solvent: dimethyl formamide 55-72%;
Antioxidant 1010: 0.1-0.3%;
Impervious aqua 0750:0.3%-0.5%.
2. according to a kind of in claim 1 fiber water-proof coating resin of ultra high modulus, it is characterized in that, in particular polyesters polyvalent alcohol for total mass, the mass content of each component of described particular polyesters polyvalent alcohol is as follows: oxalic acid 15-20%; Para Toluic Acid 30-40%, glycol ether 35-55% synthesize.
3., according to a kind of in claim 1 fiber water-proof coating resin of ultra high modulus, it is characterized in that, the preparation method of this high-rebound polyurethane resin comprises the following steps:
(1) the particular polyesters polyvalent alcohol of organic solvent and the formula ratio of part, small molecule polyol mixture, antioxidant are dropped into stirring at normal temperature in reactor simultaneously and mix, wherein, churning time must not be less than 30min;
(2) put in reactor by 4,4-diphenylmethanediisocyanates of 90% amount in formula ratio several times, and temperature of reaction controls at 70-80 DEG C, the reaction times must not be less than 120min;
(3) carry out correction thickening after having reacted in (2) step, namely add 4,4-diphenylmethanediisocyanates of remaining 10% amount in formula ratio to reactor;
(4) after reactor medium viscosity reaches 100,000 CPS/25 DEG C, start sampling and testing, after sampling and testing viscosity reaches 8-12 ten thousand CPS/25 DEG C, in reactor, add the impervious aqua of remaining organic solvent and formula ratio;
(5) repetition measurement viscosity qualified stable after carry out cooling and process, temperature controls less than 60 DEG C 40 DEG C with loading and unloading material.
4. according to a kind of in claim 3 fiber water-proof coating resin of ultra high modulus, it is characterized in that, the amount that the preparation method of this high-rebound polyurethane resin adds organic solvent in (1) step is 40% of formula ratio, the amount adding organic solvent in (4) step is 60% of formula ratio, and churning time controls at 45min in (1) step.
5. according to a kind of in claim 3 fiber water-proof coating resin of ultra high modulus, it is characterized in that, the preparation method of this high-rebound polyurethane resin in (2) step by formula ratio 90% 4,4-diphenylmethanediisocyanate divides equally three times, and every minor tick 30min drops in reactor, and in (2) step the reaction times control at 180min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510807671.3A CN105461880A (en) | 2015-11-20 | 2015-11-20 | Superhigh-modulus resin used for fiber waterproof coatings and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510807671.3A CN105461880A (en) | 2015-11-20 | 2015-11-20 | Superhigh-modulus resin used for fiber waterproof coatings and preparing method thereof |
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| CN105461880A true CN105461880A (en) | 2016-04-06 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464879A (en) * | 2010-11-10 | 2012-05-23 | 江苏东邦科技有限公司 | Polyurethane resin for high light fabric coating, and manufacture method thereof |
| CN102585685A (en) * | 2011-01-14 | 2012-07-18 | 周太峰 | Single-component polyurethane waterproof paint and preparation process thereof |
| US8829076B2 (en) * | 2010-11-19 | 2014-09-09 | Axalta Coating Systems Ip Co., Llc | Thermoset composition containing low molecular weight polytrimethylene ether glycol |
| CN104087148A (en) * | 2014-07-02 | 2014-10-08 | 常熟佳发化学有限责任公司 | High-strength polyurethane waterproof paint |
| CN104194608A (en) * | 2014-09-11 | 2014-12-10 | 北京东方雨虹防水技术股份有限公司 | Organosilane modified single-component polyurethane waterproof coating and preparation method thereof |
-
2015
- 2015-11-20 CN CN201510807671.3A patent/CN105461880A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464879A (en) * | 2010-11-10 | 2012-05-23 | 江苏东邦科技有限公司 | Polyurethane resin for high light fabric coating, and manufacture method thereof |
| US8829076B2 (en) * | 2010-11-19 | 2014-09-09 | Axalta Coating Systems Ip Co., Llc | Thermoset composition containing low molecular weight polytrimethylene ether glycol |
| CN102585685A (en) * | 2011-01-14 | 2012-07-18 | 周太峰 | Single-component polyurethane waterproof paint and preparation process thereof |
| CN104087148A (en) * | 2014-07-02 | 2014-10-08 | 常熟佳发化学有限责任公司 | High-strength polyurethane waterproof paint |
| CN104194608A (en) * | 2014-09-11 | 2014-12-10 | 北京东方雨虹防水技术股份有限公司 | Organosilane modified single-component polyurethane waterproof coating and preparation method thereof |
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Address after: 314000 Xiuzhou District, Zhejiang Province Wang Jiang Jing Development Zone Applicant after: Zhejiang Rock new material Limited by Share Ltd Address before: 314000 Xiuzhou District, Zhejiang Province Wang Jiang Jing Development Zone Applicant before: JIAXING ROCK CHEMISTRY INDUSTRY CO., LTD. |
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