CN1508167A - Method for producing unsaturated polyester resin by utilizing refuse of biatomic acid such as terephthalic acid and catalyst used thereof - Google Patents
Method for producing unsaturated polyester resin by utilizing refuse of biatomic acid such as terephthalic acid and catalyst used thereof Download PDFInfo
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- CN1508167A CN1508167A CNA021516022A CN02151602A CN1508167A CN 1508167 A CN1508167 A CN 1508167A CN A021516022 A CNA021516022 A CN A021516022A CN 02151602 A CN02151602 A CN 02151602A CN 1508167 A CN1508167 A CN 1508167A
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Abstract
The invention discloses a method to use binary ester wastes like P-phthalic acid to prepare unsaturated polyester resin, substituting fully or partly industrial waste residue containing binary acid for the binary acid to produce the unsaturated resin. It adopts stannous oxide, stannous salt or other stannous compound as catalyzer, added in effective quantity of catalyst. It largely reduces production cost and helps protect environment; besides, the new-type catalyzer can accelerate reaction velocity, able to be applied to the production of similar unsaturated resin.
Description
Technical field
The present invention relates to raw material and catalyzer that a kind of unsaturated polyester resin is produced.
Background technology
Unsaturated polyester resin has widely to be used, especially as artwork, the main raw material of rostone etc., and pure terephthalic acid (PTA) is as the main raw material(s) of terylene industrial, output both domestic and external grows with each passing day, the terephthalic acid that in its production process, is produced, m-phthalic acid, phenylformic acid etc., will be with they big cost height of separating difficulty one by one, Chinese patent CN 1073549C discloses a kind of preparation method of terephthalate, it produces when adopting industrial p xylene oxidation legal system to get terephthalic acid a large amount of terephthalic acid 50-60% that contain, phthalic acid 5-10%, the terephthalic acid by product of phenylformic acid 25-35% and aliphatic monobasic alcohol and dibasic alcohol ester are produced the terephthalic acid mixed ester.Its product is as the softening agent of polrvinyl chloride product.The using value of its product is lower.Chinese patent CN 1283645A discloses the preparation method and the unsaturated polyester resin compositions of another kind of unsaturated polyester, it utilizes recovery PET to be raw material, with after its depolymerization with maleic anhydride, make it to react to each other, add polyvalent alcohol and polyprotonic acid generation polycondensation again in mixture, its polycondensation condition it does not see open.
Summary of the invention
Primary and foremost purpose of the present invention is to utilize the PTA waste residue to prepare the method for unsaturated polyester.Another object of the present invention is the catalyzer of a kind of unsaturated dibasic acid of development and dibasic alcohol esterification reaction.
Technical scheme of the present invention is to adopt to contain the industrial residue that terephthalic acid, phthalic acid etc. contain diprotic acid, special terylene industrial is produced the waste residue of terephthalic acid, replace or partly replace diprotic acid, particularly Tetra hydro Phthalic anhydride, butene dioic acid production unsaturated polyester.
A kind of unsaturated dibasic acid of the present invention's development and the catalyzer of dibasic alcohol esterification reaction are tin protoxide, or tin salt or other stannous compound, and its addition is the significant quantity of catalyzer.
Described catalyzer addition is preferably the 1/2000-1/1000 of PTA waste residue.(weight ratio).
The PTA waste residue of described industrial residue during preferably terylene is produced, and can form all or partly replace diprotic acid according to it.
PTA waste residue amount is preferably the 0.36-0.54 of diprotic acid total amount in the described prescription;
Polyvalent alcohol can be but is not only in the described reaction: glycol ether, propylene glycol, ethylene glycol, butyleneglycol, hexylene glycol.
Described unsaturated acid can be also be not limited to be: FUMARIC ACID TECH GRADE, maleic acid and acid anhydrides.
The unsaturated polyester that obtains is dissolved in the unsaturated monomer of free redical polymerization in common mode, obtains the liquid unsaturated polyester resin composition.The unsaturated monomer of free redical polymerization includes but not limited to vinylbenzene, acrylate, methacrylic ester and phthalic acid diallyl.Select suitable unsaturated monomer according to the purposes of unsaturated polyester resin compositions and the performance of requirement.
The present invention prepares unsaturated polyester and their combination substance method can utilize the common equipment of preparation unsaturated polyester to carry out fully.
Compoundings such as unsaturated polyester resin compositions of the present invention and low type additive, filler, toughener, solidifying agent, tinting material, releasing agent, thickening material are with the preparation moulding compound.Moulding compound of the present invention shows excellent shaping characteristic, and stably produces the moulded products with high quality and good appearance.
Unsaturated polyester resin compositions of the present invention also can make to contain the matrix of glass fibre as the strong plastics in strongthener border.If desired, resin combination can mix with unsaturated polyester resin compositions or air dried unsaturated polyester resin compositions, to have improved performance or dry air performance.
The low type additive that can be used for moulding compound comprises but is not limited to thermoplastic polymer, as polystyrene, polymethylmethacrylate, polyethylene, polypropylene.
Can be used for the moulding compound filler and include but not limited to lime carbonate, aluminium hydroxide, clay, talcum powder and silicon-dioxide.Select appropriate filler according to the purposes of moulding compound and the performance of requirement.
Available solidifying agent typical case comprises organo-peroxide, as methylethyl ketone peroxide, peroxidation phenylformic acid tertiary butyl ester.Can determine the temperature of moulding and cycle to select suitable compound according to productivity by moulded products.
Can from various organic or inorganic pigment, select tinting material by color as requested, as phthalocyanine compound and titanium dioxide and analogue.Pigment is usually with the evenly form of pigment granules interpolation in being dispersed in unsaturated polyester resin of pigment.
The available stopper includes but not limited to quinhydrones, toluene hydroquinone and para benzoquinone.
The available releasing agent includes but not limited to lipid acid, as stearic acid and lauric acid, and their metal-salt.
The toughener that can be used in the moulding compound of the present invention includes but not limited to glass fibre, carbon fiber, aromatic arginyl amine fiber, and their blend fiber.
The present invention has utilized industrial residue system unsaturated polyester, and its production cost reduces greatly, and helps environment protection; Simultaneously, new catalyst of the present invention can be used for previous reaction, and fast reaction speed also can be used in the similar unsaturated polyester production.
Embodiment:
Embodiment 1: prepare reaction mass in following ratio:
PTA waste residue (mol): glycol ether (mol): FUMARIC ACID TECH GRADE: vinylbenzene=0.36: 1: 0.54: 1.62, catalyzer is chosen tin protoxide and by PTA waste residue 1/1000 consumption.
Operation steps: 1, PAT waste residue, catalyzer and glycol ether (total amount 80%) dropped in the reactor heat up, wait material dissolution after, open and stir logical nitrogen.
2, stirring is warming up to 200 ℃, and insulation reaction is also kept; The backflow column top temperature is at 105-110 ℃, and backflow 6-8 hour, liquid was from muddiness to transparent acid number 8-10.Be cooled to 150 ℃, prepare secondary batching.
The second step reaction: 1, drop into unsaturated dibasic acid and remaining saturated dibasic alcohol, heat up then by prescription, wait material to dissolve after, logical nitrogen.
2, be warming up to 200 ℃ of insulations 2 hours, sampling detecting acid number is 45+3 until acid number.
3, vacuumize the reaction of reducing pressure, make acid number reduce to 25+2, be cooled to 180 ℃, add stopper and paraffin, open stirrer and continue to be cooled to 130 ℃, prepare blowing.
At last, polymkeric substance is slowly put into vinylbenzene dilute, temperature is controlled between the 70-80 ° of C.Stir half an hour, be cooled to 45 ℃, filter, packing, finished product warehouse-in.
Embodiment 2: prepare reaction mass in following ratio:
PTA waste residue (mol): glycol ether (mol): FUMARIC ACID TECH GRADE: vinylbenzene=0.41: 1: 0.50: 1.38, catalyzer is chosen tin protoxide and by PTA waste residue 1/1000 consumption.
Operation steps is the same.
Embodiment 3: prepare reaction mass in following ratio:
PTA waste residue (mol): glycol ether (mol): FUMARIC ACID TECH GRADE: vinylbenzene=0.45: 1: 0.45: 1.15, catalyzer is chosen tin protoxide and by PTA waste residue 1/1000 consumption.
Operation steps is with embodiment 1.
Embodiment 4:
Prepare reaction mass in following ratio:
PTA waste residue (mol): glycol ether (mol): FUMARIC ACID TECH GRADE: vinylbenzene=0.50: 1: 0.41: 1.05, catalyzer is chosen tin protoxide and by PTA waste residue 1/1000 consumption.
Working method is with embodiment 1.
Embodiment 5:
Prepare reaction mass in following ratio:
PTA waste residue (mol): glycol ether (mol): FUMARIC ACID TECH GRADE: vinylbenzene=0.54: 1: 0.36: 0.9, catalyzer is chosen tin protoxide or stannous sulfate and by PTA waste residue 1/1000 consumption.
Working method is with embodiment 1.
PTA waste residue of the present invention and glycol ether ester are reflected at 8 hours and just can finish, and the unsaturated polyester body of casting performance of generation is up to state standards Ba Keer hardness＞35
Claims (11)
1, a kind of method of utilizing diprotic acid waste residue production unsaturated polyester resins such as terephthalic acid, by unsaturated dibasic acid and the preparation of dibasic alcohol esterification reaction, it is characterized in that adopting the industrial residue that contains terephthalic acid, phthalic acid, replace or partly replace diprotic acid, the production unsaturated polyester.
2, a kind of unsaturated dioctyl phthalate and dibasic alcohol ester are answered catalyst for reaction, it is characterized in that used catalyzer is a tin protoxide, or tin salt or other stannous compound, and its addition is the significant quantity of catalyzer.
3, a kind of catalyzer that utilizes terephthalic acid (PTA) waste residue to produce unsaturated polyester resin according to claim 2 is characterized in that the catalyzer addition is the 1/2000-1/1000 (weight ratio) of PTA waste residue.
4, a kind of method of utilizing terephthalic acid (PTA) waste residue to produce unsaturated polyester resin according to claim 1 is characterized in that diprotic acid be formed all or partly be replaced to the PTA waste residue can according to its content in the described prescription.
5,1 described a kind of method of utilizing diprotic acid waste residue such as terephthalic acid to produce unsaturated polyester resins as requested, PTA waste residue amount is the 0.36-0.54 of diprotic acid total amount in the described prescription of its feature.
6,1 described a kind of method of utilizing diprotic acid waste residue such as terephthalic acid to produce unsaturated polyester resins as requested, polyvalent alcohol can be in the described reaction of its feature: glycol ether, propylene glycol, ethylene glycol, butyleneglycol, hexylene glycol.
7,1 described a kind of method of utilizing diprotic acid waste residue such as terephthalic acid to produce unsaturated polyester resins as requested, it is characterized in that described unsaturated acid can: FUMARIC ACID TECH GRADE, maleic acid and acid anhydrides.
8,1 described a kind of method of utilizing diprotic acid waste residue such as terephthalic acid to produce unsaturated polyester resins as requested, it is characterized in that the unsaturated polyester that will obtain is dissolved in the unsaturated monomer of free redical polymerization in common mode, obtains the liquid unsaturated polyester resin composition.
9,1 or 8 described a kind of methods of utilizing diprotic acid waste residue such as terephthalic acid to produce unsaturated polyester resins as requested is characterized in that unsaturated monomer vinylbenzene, acrylate, methacrylic ester and the phthalic acid diallyl of free redical polymerization.
10,1 described a kind of method of utilizing diprotic acid waste residue such as terephthalic acid to produce unsaturated polyester resins as requested is characterized in that concrete reaction ratio is as follows:
PTA waste residue (mol): glycol ether (mol): FUMARIC ACID TECH GRADE: vinylbenzene=0.36-0.54: 1: 0.54-0.36: 1.38-0.9, catalyzer choose tin protoxide and by PTA waste residue 1/1000 consumption.
11,1 described a kind of method of utilizing diprotic acid waste residue such as terephthalic acid to produce unsaturated polyester resins as requested is characterized in that concrete reactions steps is as follows:
Operation steps: (1), 80% of PAT waste residue, catalyzer and glycol ether total amount dropped in the reactor heat up, wait material dissolution after, open and stir logical nitrogen;
(2), stir and to be warming up to 200 ℃, insulation reaction is also kept; The backflow column top temperature is at 105-110 ℃, and backflow 6-8 hour, liquid was from muddiness to transparent acid number 8-10.Be cooled to 150 ℃, prepare secondary batching;
The second step reaction: (1), drop into unsaturated dibasic acid and remaining saturated dibasic alcohol by prescription, heat up then, wait material to dissolve after, logical nitrogen;
(2), be warming up to 200 ℃ the insulation 2 hours, sampling detecting acid number is 4 5+3 until acid number;
(3), vacuumize the reaction of reducing pressure, make acid number reduce to 25+2, be cooled to 180 ℃, add stopper and paraffin, open stirrer and continue to be cooled to 130 ℃, prepare blowing;
At last, polymkeric substance is slowly put into vinylbenzene dilute, temperature is controlled between the 70-80 ° of C; Stir half an hour, be cooled to 45 ℃, filter, packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021516022A CN1508167A (en) | 2002-12-19 | 2002-12-19 | Method for producing unsaturated polyester resin by utilizing refuse of biatomic acid such as terephthalic acid and catalyst used thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021516022A CN1508167A (en) | 2002-12-19 | 2002-12-19 | Method for producing unsaturated polyester resin by utilizing refuse of biatomic acid such as terephthalic acid and catalyst used thereof |
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| CN1508167A true CN1508167A (en) | 2004-06-30 |
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| CNA021516022A Pending CN1508167A (en) | 2002-12-19 | 2002-12-19 | Method for producing unsaturated polyester resin by utilizing refuse of biatomic acid such as terephthalic acid and catalyst used thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453577C (en) * | 2006-03-23 | 2009-01-21 | 华东理工大学华昌聚合物有限公司 | Process for producing terephthalic unsaturated polyester resin by using terephthalic acid rinsing residue |
| CN102432769A (en) * | 2011-07-25 | 2012-05-02 | 漳州亚邦化学有限公司 | Unsaturated polyester resin and production method thereof |
| CN103265668A (en) * | 2013-05-21 | 2013-08-28 | 山东宏信化工股份有限公司 | Preparation method of terephthalic type unsaturated polyester resin |
| CN106317392A (en) * | 2016-08-29 | 2017-01-11 | 福建梭罗复合材料研究有限公司 | High-weather-resistant unsaturated polyester resin prepared from extinction polyester waste and preparation method thereof |
| CN106432622A (en) * | 2016-09-27 | 2017-02-22 | 辽阳合成催化剂有限公司 | Method for preparing unsaturated polyester resin from reclaimed material containing saturated binary acid |
| CN106633585A (en) * | 2016-12-01 | 2017-05-10 | 安徽星元环保科技有限公司 | High-quality unsaturated resin for artificial quartz basin |
| CN110023266A (en) * | 2016-12-08 | 2019-07-16 | 阿肯马法国公司 | Curing agent for curable polymer resin |
-
2002
- 2002-12-19 CN CNA021516022A patent/CN1508167A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453577C (en) * | 2006-03-23 | 2009-01-21 | 华东理工大学华昌聚合物有限公司 | Process for producing terephthalic unsaturated polyester resin by using terephthalic acid rinsing residue |
| CN102432769A (en) * | 2011-07-25 | 2012-05-02 | 漳州亚邦化学有限公司 | Unsaturated polyester resin and production method thereof |
| CN102432769B (en) * | 2011-07-25 | 2013-02-27 | 漳州亚邦化学有限公司 | Unsaturated polyester resin and production method thereof |
| CN103265668A (en) * | 2013-05-21 | 2013-08-28 | 山东宏信化工股份有限公司 | Preparation method of terephthalic type unsaturated polyester resin |
| CN103265668B (en) * | 2013-05-21 | 2015-08-12 | 山东宏信化工股份有限公司 | The preparation method of terephthalic unsaturated polyester resin |
| CN106317392B (en) * | 2016-08-29 | 2018-02-09 | 福建梭罗复合材料研究有限公司 | High durable unsaturated polyester resin and preparation method are prepared with delustring terylene waste |
| CN106317392A (en) * | 2016-08-29 | 2017-01-11 | 福建梭罗复合材料研究有限公司 | High-weather-resistant unsaturated polyester resin prepared from extinction polyester waste and preparation method thereof |
| CN106432622A (en) * | 2016-09-27 | 2017-02-22 | 辽阳合成催化剂有限公司 | Method for preparing unsaturated polyester resin from reclaimed material containing saturated binary acid |
| CN106432622B (en) * | 2016-09-27 | 2019-01-01 | 辽阳合成催化剂有限公司 | A method of reclaimed materials containing monounsaturated dicarboxylic acid prepares unsaturated polyester resin |
| CN106633585A (en) * | 2016-12-01 | 2017-05-10 | 安徽星元环保科技有限公司 | High-quality unsaturated resin for artificial quartz basin |
| CN106633585B (en) * | 2016-12-01 | 2019-06-11 | 安徽星元环保科技有限公司 | A kind of high-quality unsaturated-resin of synthetic quartz basin |
| CN110023266A (en) * | 2016-12-08 | 2019-07-16 | 阿肯马法国公司 | Curing agent for curable polymer resin |
| CN110023266B (en) * | 2016-12-08 | 2022-09-13 | 阿肯马法国公司 | Curing agent for curing polymer resins |
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