CN102432854A - Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer - Google Patents
Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer Download PDFInfo
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- CN102432854A CN102432854A CN201110255077XA CN201110255077A CN102432854A CN 102432854 A CN102432854 A CN 102432854A CN 201110255077X A CN201110255077X A CN 201110255077XA CN 201110255077 A CN201110255077 A CN 201110255077A CN 102432854 A CN102432854 A CN 102432854A
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- polyester plasticizer
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Abstract
The invention discloses a polyester plasticizer for leading glass fiber to form a felt and a preparation method of the polyester plasticizer. The polyester plasticizer is prepared from dihydric alcohol and dibasic acid. The preparation method comprises the following steps of: 1) adding the dihydric alcohol and the dibasic acid into a reactor, introducing nitrogen, stirring, rising the temperature to be 200-220 DEG C, and under the temperature, reacting till the acid value of the system is less than or equal to 20mgKOH/g; and 2) reducing the temperature to be 180-190 DEG C, adding hydroquinone, cooling to be 0-40 DEG C, filtering, and obtaining filtrate, i.e. the polyester plasticizer; or directly cooling to be 0-40 DEG C, filtering, and obtaining filtrate, i.e. the polyester plasticizer. In the invention, the compatibility of the polyester plasticizer and a bonding agent for leading the glass fiber to form the felt is good, the softness and the impregnability of a glass-fiber chopped felt can be improved and the use range is wide.
Description
Technical field
The present invention relates to a kind of polyester plasticizer and preparation method thereof, be specifically related to a kind of spun glass and become felt with polyester plasticizer and preparation method thereof.
Background technology
Glass chopped strand mats is with short certain-length and the omnidirectional at random uniform distribution of being cut into of glass fiber precursor (or roving), applies suitable Chemical Felter then, again the felted product through drying, colding pressing, cool off and process.Glass chopped strand mats also has the characteristic of many excellences except keeping spun glass inherent characteristic.The internal performance of glass chopped strand mats mainly comprises intensity, flexibility and the impregnability of felt, and the short principal element of cutting the felt internal performance of influence is the treating compound of using in the precursor moulding process and the short sticker of using in the felt moulding process of cutting.
Wherein produce the used sticker of glass chopped strand mats and play important effect guaranteeing and improving short performance of cutting felt.Sticker commonly used at present comprises powder adhesive and emulsion binder.Wherein powder adhesive only has sticker on the point of crossing of glass fiber yarn partly, and bonding point is few, falls yarn easily.And that the characteristics of emulsion binder are bond state is good, is not easy yarn, easy to use, is well suited for mechanical continuous forming process, and intensity is high and non-directional.And emulsion binder is accomplished than being easier on the intensity that guarantees felt, but is guaranteeing will to accomplish that flexibility and impregnability well then are not easy on the felt intensity based.In emulsion binder, add softening agent and then can improve short flexibility and impregnability of cutting felt, this is because the adding of softening agent greatly reduces the second-order transition temperature of polymer emulsion, has improved the elongation at break and the tensile strength of polymer emulsion.
Softening agent commonly used in the industry has O-phthalic acids softening agent and phosphate plasticizer etc., and these softening agent are oil soluble, become felt poor with the compatibility of sticker with spun glass, even reduce the impregnability of fiberglass products sometimes.
Chinese patent document CN100387632C discloses a kind of working method of mixed polyester plasticizer; This mixed polyester plasticizer obtains work in-process by the first esterification under the effect of nonacid catalyst for esterification reaction of polyvalent alcohol, monohydroxy-alcohol and polyprotonic acid, and then in the presence of the metal acetate saline catalyst, carries out transesterification reaction with monohydroxy-alcohol and monacid mixed ester and obtain polyester plasticizer.The deficiency of this patent is: complex process, raw material is more, need a large amount of catalyzer, and molecular weight is very big, does not have snappiness, is inappropriate for spun glass and becomes felt to use.
Chinese patent document CN101735756A discloses a kind of polyester resin emulsion binding agent for glass fiber mat; This sticker comprises vibrin or its mixture, nonionic emulsifier, linking agent and water, and wherein vibrin or its mixture account for 60%～93% of sticker gross weight.The deficiency of this patent is: (1) this patent is directly processed emulsion with polyprotonic acid and polyvalent alcohol and nonionic emulsifier, processes sticker with linking agent again, has dwindled its use range so greatly.(2) diprotic acid that adopts mainly still is a phthalic acid, and still existence becomes the shortcoming of felt with sticker compatibility difference with spun glass.
Summary of the invention
One of the object of the invention is to address the above problem, and a kind of flexibility and impregnability that felt is good with the sticker compatibility, can improve glass chopped strand mats that become with spun glass is provided, and the spun glass that use range is wide becomes felt to use polyester plasticizer.
Another object of the present invention is to provide the preparation method of above-mentioned polyester plasticizer.
The technical scheme that realizes one of the object of the invention is: a kind of spun glass becomes felt to use polyester plasticizer, is processed by divalent alcohol and diprotic acid; Described divalent alcohol is that glycol ether perhaps is any in glycol ether and terepthaloyl moietie, Ucar 35, the polyoxyethylene glycol; Described diprotic acid is hexanodioic acid or is hexanodioic acid and MALEIC ANHYDRIDE; The number-average molecular weight of this polyester plasticizer is that 1000～6000,25 ℃ of measured viscosity are 0.1Pas～8.0Pas.
The number-average molecular weight of this polyester plasticizer is 1000～2000, and viscosity is 0.1Pas～1.0Pas.
The mol ratio of described divalent alcohol and diprotic acid is 1: 1～1.8: 1.
Described divalent alcohol is a glycol ether, and described diprotic acid is a hexanodioic acid.
The technical scheme that realizes another purpose of the present invention is: a kind of spun glass becomes the preparation method of felt with polyester plasticizer; Have following steps: 1. in reactor drum, add divalent alcohol and diprotic acid; Feeding nitrogen and stirring are warming up to 200 ℃～220 ℃, under this temperature, react to system acid number≤20mgKOH/g; Described divalent alcohol is that glycol ether perhaps is any in glycol ether and terepthaloyl moietie, Ucar 35, the polyoxyethylene glycol; Described diprotic acid is hexanodioic acid or is hexanodioic acid and MALEIC ANHYDRIDE; 2. be cooled to 180 ℃～190 ℃, add Resorcinol, be cooled to 0 ℃～40 ℃ then, filter, filtrating is polyester plasticizer; Perhaps directly be cooled to 0 ℃～40 ℃, filter, filtrating is polyester plasticizer.
The mol ratio of described divalent alcohol and diprotic acid is 1: 1～1.8: 1.
Described divalent alcohol is a glycol ether, and described diprotic acid is a hexanodioic acid.
The positively effect that the present invention has: (1) because spun glass becomes felt to be the emulsion polymerization or the aqueous solution with the various membrane components that are bonded to of sticker, its matrix resin is generally vibrin, PVAc resin, epoxy resin or urethane resin.And the polyester plasticizer that the present invention makes and they have splendid consistency, and SP is also very approaching, improves the adhesive property of spun glass monofilament so greatly, improve the flexibility and the impregnability of glass chopped strand mats.Adopt the wetting-out rate of glass chopped strand mats of this type of plasticizer production fast, and can solidify simultaneously with matrix resin, interface junction gets togather, and the ageing-resistant performance of FRP goods is good.(2) polyester plasticizer of the present invention does not contain adjacent benzene class material, and is nontoxic, cheap, and number-average molecular weight is high, than monomerics have that migration is little, high temperature resistant, volatilization less, be not easy by advantages such as water and solvent extractions.(3) polyester plasticizer of the present invention also has the performance adjustability, promptly as long as change the kind and the proportioning of divalent alcohol and diprotic acid, just can make the different polyester plasticizer of plasticization effect.Particularly along with the increasing of molar ratio of alcohol to acid, the molecular weight of the polyester plasticizer that makes can diminish, and the viscosity of resin then diminishes, and then improves with the consistency of polymer emulsion, and plasticizing efficiency improves greatly.(4) polyester plasticizer of the present invention can be used in combination with emulsion binder; And can produce that different model, performance are different according to demands of different, the composite emulsion of high solids content, high impregnability; Improved the scope of application greatly; Solid content reaches as high as about 62%, and excellent storage stability, have that cohesive strength is good, impregnability is fast, in soft, the felt process of felt face the guipure skinning few, be easy to advantage such as cleaning.
Embodiment
(embodiment 1)
The spun glass of present embodiment becomes felt to be processed by glycol ether, terepthaloyl moietie, hexanodioic acid and MALEIC ANHYDRIDE with polyester plasticizer, and its number-average molecular weight is 1200, and viscosity is 0.50～0.60 (Pas, 25 ℃).
The preparation method of this polyester plasticizer has following steps:
1. in reactor drum, add glycol ether 850g, terepthaloyl moietie 140g, hexanodioic acid 580g, MALEIC ANHYDRIDE 220g; Feed nitrogen and stir and be warming up to 210 ℃ gradually; Reaction system becomes and keeps behind the homogeneous transparent temperature to continue reaction again, until recording acid number less than 12mgKOH/g.
2. be cooled to 190 ℃, add Resorcinol 162g, be cooled to 0 ℃～40 ℃ then, filter, filtrating is polyester plasticizer, and weight is 1610g, and number-average molecular weight is 1200.Its outward appearance is light yellow thick liquid, and acid number is 8～12mgKOH/g, and viscosity is 0.50～0.60 (Pas, 25 ℃).
(embodiment 2)
Present embodiment and embodiment 1 are basic identical, and difference is seen table 1.
(embodiment 3)
Step among the preparation method of present embodiment is 1. basic identical with embodiment 1, and step is 2. following:
2. be cooled to 0 ℃～40 ℃, filter, filtrating is ester plasticizer.Its outward appearance is light yellow thick liquid.All the other differences are seen table 1.
(embodiment 4)
Present embodiment basic identical with embodiment 1, difference is seen table 1.
The typical quality index of above-mentioned each embodiment resulting polyester softening agent is seen table 1:
Table 1
Claims (7)
1. a spun glass becomes felt to use polyester plasticizer, is processed by divalent alcohol and diprotic acid; It is characterized in that: described divalent alcohol is that glycol ether perhaps is any in glycol ether and terepthaloyl moietie, Ucar 35, the polyoxyethylene glycol; Described diprotic acid is hexanodioic acid or is hexanodioic acid and MALEIC ANHYDRIDE; The number-average molecular weight of this polyester plasticizer is that 1000～6000,25 ℃ of measured viscosity are 0.1Pas～8.0Pas.
2. spun glass according to claim 1 becomes felt to use polyester plasticizer, it is characterized in that: the number-average molecular weight of this polyester plasticizer is 1000～2000, and viscosity is 0.1Pas～1.0Pas.
3. spun glass according to claim 1 and 2 becomes felt to use polyester plasticizer, it is characterized in that: the mol ratio of described divalent alcohol and diprotic acid is 1: 1～1.8: 1.
4. spun glass according to claim 3 becomes felt to use polyester plasticizer, it is characterized in that: described divalent alcohol is a glycol ether, and described diprotic acid is a hexanodioic acid.
5. claim 1 or 2 described spun glass become the preparation method of felt with polyester plasticizer, it is characterized in that having following steps:
1. in reactor drum, add divalent alcohol and diprotic acid, feeding nitrogen and stirring are warming up to 200 ℃～220 ℃, under this temperature, react to system acid number≤20mgKOH/g; Described divalent alcohol is that glycol ether perhaps is any in glycol ether and terepthaloyl moietie, Ucar 35, the polyoxyethylene glycol; Described diprotic acid is hexanodioic acid or is hexanodioic acid and MALEIC ANHYDRIDE;
2. be cooled to 180 ℃～190 ℃, add Resorcinol, be cooled to 0 ℃～40 ℃ then, filter, filtrating is polyester plasticizer;
Perhaps directly be cooled to 0 ℃～40 ℃, filter, filtrating is polyester plasticizer.
6. spun glass according to claim 5 becomes the preparation method of felt with polyester plasticizer, it is characterized in that: the mol ratio of described divalent alcohol and diprotic acid is 1: 1～1.8: 1.
7. spun glass according to claim 6 becomes the preparation method of felt with polyester plasticizer, it is characterized in that: described divalent alcohol is a glycol ether, and described diprotic acid is a hexanodioic acid.
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| CN201110255077.XA CN102432854B (en) | 2011-08-31 | 2011-08-31 | Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer |
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| CN201110255077.XA CN102432854B (en) | 2011-08-31 | 2011-08-31 | Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer |
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| CN102432854A true CN102432854A (en) | 2012-05-02 |
| CN102432854B CN102432854B (en) | 2014-02-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031250A (en) * | 2014-06-17 | 2014-09-10 | 常州天马集团有限公司（原建材二五三厂） | Method for preparing carrier resin for unsaturated polyester resin mill base |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668696A (en) * | 2002-06-18 | 2005-09-14 | 佐治亚-太平洋树脂公司 | Polyester-type formaldehyde free insulation binder |
| CN101245230A (en) * | 2008-02-21 | 2008-08-20 | 上海天洋热熔胶有限公司 | Method for manufacturing linear copolyester hot melt adhesive |
| CN101735756A (en) * | 2010-01-27 | 2010-06-16 | 南京彤天科技实业有限责任公司 | Polyester resin emulsion binding agent for glass fiber mat |
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2011
- 2011-08-31 CN CN201110255077.XA patent/CN102432854B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668696A (en) * | 2002-06-18 | 2005-09-14 | 佐治亚-太平洋树脂公司 | Polyester-type formaldehyde free insulation binder |
| CN101245230A (en) * | 2008-02-21 | 2008-08-20 | 上海天洋热熔胶有限公司 | Method for manufacturing linear copolyester hot melt adhesive |
| CN101735756A (en) * | 2010-01-27 | 2010-06-16 | 南京彤天科技实业有限责任公司 | Polyester resin emulsion binding agent for glass fiber mat |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031250A (en) * | 2014-06-17 | 2014-09-10 | 常州天马集团有限公司（原建材二五三厂） | Method for preparing carrier resin for unsaturated polyester resin mill base |
| CN104031250B (en) * | 2014-06-17 | 2016-06-01 | 常州天马集团有限公司（原建材二五三厂） | The preparation method of unsaturated polyester resin mill base vector resin |
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| CN102432854B (en) | 2014-02-05 |
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Owner name: CHANGZHOU TIANMA GROUP CO., LTD. (BUILDING TWO FIV Free format text: FORMER NAME: TIANMO GROUP CO., LTD., CHANGZHOU |
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Address after: 213127 No. 309 Huang Hai Road, Xinbei District, Jiangsu, Changzhou Patentee after: Changzhou Tianma Group Co., Ltd. (former building material 253 factory) Address before: 213002 No. 501 ERON North Road, Xinbei District, Jiangsu, Changzhou Patentee before: Tianmo Group Co., Ltd., Changzhou |