CN101508828B - Saturated polyester resin for molding compound as shrinking agent and production method thereof - Google Patents
Saturated polyester resin for molding compound as shrinking agent and production method thereof Download PDFInfo
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- CN101508828B CN101508828B CN2009100103558A CN200910010355A CN101508828B CN 101508828 B CN101508828 B CN 101508828B CN 2009100103558 A CN2009100103558 A CN 2009100103558A CN 200910010355 A CN200910010355 A CN 200910010355A CN 101508828 B CN101508828 B CN 101508828B
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Abstract
The invention relates to a low shrinkage agent used for molding compound. Saturated polyester resin used for molding compound low shrinkage agent is prepared by dissolving propanediol, glycol and the polymer of dipropylene glycol and aliphatic dibasic acid in styrene. The low shrinkage agent has the advantages that (1) the dipropylene glycol is used for synthesizing the saturated polyester resin to ensure that the resin has good water resistance and flexibility, and a product has good moisture-resistant ability and good mechanical property; (2) the low shrinkage agent produced by the dipropylene glycol has strong adaptability, can be matched with various molding compound resins and can ensure that the product reaches zero shrinkage and ensure the accuracy of the size of the product; and (3) the aliphatic dibasic acid is used for replacing aromatic dibasic acid, and in particular m-phthalic acid can shorten the reaction time to reduce energy consumption and also can increase the aging resistance of the molding compound product.
Description
Technical field
The invention belongs to the macromolecule chemical industry field, especially for low shrinkage agent used for molding compound; Also relate to its preparation method in addition.
Background technology
Development through decades, glass fiber reinforced plastics product begins to transfer to the high mold pressing production of mechanization degree from traditional making by hand, the efficient of producing and the stability of quality product are greatly enhanced, and the requirement to unsaturated polyester resin also has very high requirement certainly.The resin great majority that originally were used for the hand paste can not satisfy the requirement of mold pressing, and not enough as the reactive behavior of resin, the shrinking percentage behind the resin solidification is excessive.The active big resin of resin can be used to produce moulding compound substantially at present, for the shrinking percentage that solves resin excessive, general many being dissolved in polystyrene done low shrinkage agent used for molding compound in the styrene solution, the advantage of this shrinking agent has: 1. tint permanence is good, can do the moulding compound of most of colors; 2. the effect that has certain control to shrink, the moulding compound product is after mold pressing, and shrinking percentage can be controlled at about 0.5%, meets the dimensional requirement general-use article.But at auto parts machinery and have on the high goods such as electric type switch of requirement of withstand voltage, because the precision requirement of its size is high especially, the shrinking percentage of mould and goods must be controlled at 0.1-0.2%, and it is powerless that this shrinking agent just seems; The shrinking agent that saturated tree lipid is also arranged now, mainly be to synthesize with propylene glycol, ethylene glycol and m-phthalic acid, hexanodioic acid, shrinking percentage also can reach the requirement of the said products, but weak point has: 1. the long reaction time of resin (cause of m-phthalic acid), 2. the goods of black class can only be produced, white products can not be done.
Summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem, a kind of saturated polyester resin that is used for molding compound as shrinking agent is provided, shrinking percentage is less than thousandth and have mechanical property preferably, is widely used.The present invention also provides its method for making,
The technical scheme that the present invention is adopted for achieving the above object is: a kind of saturated polyester resin that is used for molding compound as shrinking agent is dissolved in vinylbenzene and is made by the polymkeric substance of propylene glycol, ethylene glycol, dipropylene glycol and aliphatic dibasic acid.
Described aliphatic dibasic acid is Succinic Acid and hexanodioic acid mixture.
Described resin is formulated by following materials based on weight:
Propylene glycol 70-82
Dipropylene glycol 55-61
Ethylene glycol 38-43
Succinic Acid 44-50
Hexanodioic acid 246-252
Vinylbenzene 580-610.
It is formulated by following materials based on weight that described resin is filled a prescription preferably:
Propylene glycol 76-81
Dipropylene glycol 57-61
Ethylene glycol 40-42
Succinic Acid 46-50
Hexanodioic acid 248-252
Vinylbenzene 591-608.
The prescription of described resin the best is formulated by following materials based on weight:
Propylene glycol 81
Dipropylene glycol 57
Ethylene glycol 40
Succinic Acid 49
Hexanodioic acid 249
Vinylbenzene 597.
The method for making of shrinking agent saturated resin of the present invention, concrete steps are: propylene glycol, dipropylene glycol, ethylene glycol, Succinic Acid and hexanodioic acid are joined in the reactor that has backflow and whipping appts, stirring is warming up to water outlet, control is heated up in a steamer a temperature and is no more than 103 ℃, temperature of reaction is no more than 220 ℃, until acid number at 6-8mgKOH/g, after cooling to 160 ℃, reactant is poured in the container of styrene solution and stirred, the control of the temperature of resin is no more than 90 ℃ during agitation and dilution, makes the saturated resin that is used for molding compound as shrinking agent.
Saturated resin of the present invention is synthetic by aliphatic dibasic acid and dibasic alcohol, adopted dibasic alcohol---the dipropylene glycol of in production of resins, seldom using in the prescription both at home and abroad, contain ehter bond in the dipropylene glycol, in resin, can not only improve the toughness of resin, and the reactance voltage of resin does not reduce because of the existence of ehter bond yet, mainly be because methyl is arranged, can play a protective role on the next door of ehter bond; The 2nd, with aliphatic dicarboxylic acid substitution aromatic acid (acid anhydride), compare as raw material with traditional use aromatic acid (acid anhydride), have only aliphatic dibasic acid not have aromatic acid (acid anhydride) when synthetic, though its molecular weight is big, but after being dissolved in solvent, viscosity ratio has the saturated resin of aromatic acid (acid anhydride) to be much smaller, and it is strong that fiber soaks into ability; So not only can shorten the reaction times of production of resins, the molecular chain length of the resin that main is generates strengthens and narrowed width, when goods hot pressing in the easier slit that is penetrated into resin and resin, the shrinking percentage of end article is descended, thus the requirement of the tolerance range that improves goods when satisfying the goods design.The 3rd, with part Succinic Acid and adipic acid mixture, the rigidity effects to resin is very little simultaneously can to guarantee the resin flexible in binary acid.
Bright saturated resin that makes of the present invention and unsaturated polyester match when producing moulding compound, it is good to have with the unsaturated polyester consistency, soak into advantages such as the fiber ability is strong, because the length of saturated resin molecule is big with the width ratio, enter the space that unsaturated polyester and vinylbenzene forms when crosslinked and remedy the contraction that brings behind the resin solidification easilier, therefore make the shrinking percentage of pressing less than thousand molecules below one, satisfy the index of the high goods of dimensional requirement.Aspect painted, the saturated resin of producing with aliphatic dibasic acid (acid anhydride) can only black can not white, and saturated resin provided by the invention is good especially to the consistency of white when using as shrinking agent, and saturated resin is as the deficiency of shrinking agent before having remedied.Saturated resin of the present invention can be widely used in the high electrical equipment of dimensional requirement, automobile and other industries.
It is short that preparation technology of the present invention has the reaction times, processing ease, advantage such as the low and molecular-weight average of the acid number of polyester is longer.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but the invention is not restricted to specific embodiment.
Embodiment 1:
Prepare a kind of saturated polyester resin that is used for molding compound as shrinking agent by following composition of raw materials and method for making, filling a prescription is:
Propylene glycol 70g
Dipropylene glycol 56g
Ethylene glycol 43g
Succinic Acid 44g
Hexanodioic acid 252g
Vinylbenzene 580g
Method for making: (1) adds propylene glycol, dipropylene glycol, ethylene glycol, Succinic Acid and hexanodioic acid in the 1000ml four-hole bottle;
(2) stirring is warming up to 160 ℃, insulation 30-40min;
(3) water outlet, control is heated up in a steamer a temperature and is no more than 103 ℃, and temperature of reaction is no more than 220 ℃;
(4) 3 hours sampling and testings after the water outlet, until acid number at 8-10mgKOH/g;
(5) cool to 160 ℃ after, with reactant in the container of going into to have styrene solution;
(6) stir, the control of the temperature of resin is no more than 90 ℃ during dilution, makes the saturated resin that is used for molding compound as shrinking agent.
Embodiment 2
Prepare a kind of saturated polyester resin that is used for molding compound as shrinking agent by embodiment 1 method for making, concrete composition of raw materials is:
Propylene glycol 82g
Dipropylene glycol 60g
Ethylene glycol 39g
Succinic Acid 50g
Hexanodioic acid 246g
Vinylbenzene 610g
Embodiment 1,2 prepared saturated resin Performance Detection data such as following tables:
Because this resin is a saturated resin, does not do the test of gelation time.
Embodiment 3:
Prepare a kind of saturated polyester resin that is used for molding compound as shrinking agent by embodiment 1 method for making, concrete composition of raw materials is:
Propylene glycol 78g
Dipropylene glycol 61g
Ethylene glycol 42g
Succinic Acid 46g
Hexanodioic acid 250g
Vinylbenzene 591g.
Embodiment 4
Prepare a kind of saturated polyester resin that is used for molding compound as shrinking agent by embodiment 1 method for making, concrete composition of raw materials is:
Propylene glycol 81g
Dipropylene glycol 58g
Ethylene glycol 41g
Succinic Acid 48g
Hexanodioic acid 248g
Vinylbenzene 600g
Embodiment 3,4 prepared saturated resin Performance Detection data such as following tables:
Embodiment 5:
Prepare a kind of saturated polyester resin that is used for molding compound as shrinking agent by embodiment 1 method for making, concrete composition of raw materials is:
Propylene glycol 81g
Dipropylene glycol 57g
Ethylene glycol 40g
Succinic Acid 49g
Hexanodioic acid 249g
Vinylbenzene 597g
Prepared saturated resin Performance Detection data such as following table:
Saturated polyester resin by the foregoing description 1-5 prescription is made when producing moulding compound, is equipped with suitable molding compound resins, the pressing of making, and its shrinking percentage all can meet the requirement of zero shrinking die plastics less than thousandth.
Claims (4)
1. mixture that is used for molding compound as shrinking agent is characterized in that: be dissolved in vinylbenzene and made by the polymkeric substance of propylene glycol, ethylene glycol, dipropylene glycol and aliphatic dibasic acid; Described aliphatic dibasic acid is Succinic Acid and hexanodioic acid mixture; The parts by weight of raw materials proportioning of described mixture is:
Propylene glycol 70-82
Dipropylene glycol 55-61
Ethylene glycol 38-43
Succinic Acid 44-50
Hexanodioic acid 246-252
Vinylbenzene 580-610.
2. a kind of mixture that is used for molding compound as shrinking agent according to claim 1 is characterized in that: the parts by weight of raw materials proportion optimization of described mixture is:
Propylene glycol 76-81
Dipropylene glycol 57-61
Ethylene glycol 40-42
Succinic Acid 46-50
Hexanodioic acid 248-252
Vinylbenzene 591-608.
3. a kind of mixture that is used for molding compound as shrinking agent according to claim 2 is characterized in that: the parts by weight of raw materials proportion optimization of described mixture is:
Propylene glycol 81
Dipropylene glycol 57
Ethylene glycol 40
Succinic Acid 49
Hexanodioic acid 249
Vinylbenzene 597.
4. according to claim 1 or 2 or 3 arbitrary described a kind of method for makings that are used for the mixture of molding compound as shrinking agent, it is characterized in that: with propylene glycol, dipropylene glycol, ethylene glycol, Succinic Acid and hexanodioic acid join in the reactor that has backflow and whipping appts, stirring is warming up to water outlet, control is heated up in a steamer a temperature and is no more than 103 ℃, temperature of reaction is no more than 220 ℃, until acid number at 6-8mgKOH/g, after cooling to 160 ℃, reactant is poured in the container of styrene solution and stirred, the control of the temperature of resin is no more than 90 ℃ during agitation and dilution, makes the mixture that is used for molding compound as shrinking agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100103558A CN101508828B (en) | 2009-02-11 | 2009-02-11 | Saturated polyester resin for molding compound as shrinking agent and production method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100103558A CN101508828B (en) | 2009-02-11 | 2009-02-11 | Saturated polyester resin for molding compound as shrinking agent and production method thereof |
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| Publication Number | Publication Date |
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| CN101508828A CN101508828A (en) | 2009-08-19 |
| CN101508828B true CN101508828B (en) | 2011-07-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102206311B (en) * | 2011-04-22 | 2013-01-30 | 常州华科树脂有限公司 | Saturated polyester for sheet moulding compound or bulk molding compound (SMC/BMC) low-shrinking agent and preparation method thereof |
| CN108192087A (en) * | 2018-01-12 | 2018-06-22 | 宜兴市兴合树脂有限公司 | Mould pressing process low shrink resin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997033942A1 (en) * | 1996-03-12 | 1997-09-18 | Nippon Shokubai Co., Ltd. | Unsaturated polyester resin composition and sheetlike molding material |
| EP0982327A1 (en) * | 1998-08-21 | 2000-03-01 | Sartomer Company Inc. | Unsaturated polyester resin compositions comprising metallic monomers |
| CN1367202A (en) * | 2002-02-10 | 2002-09-04 | 颜科 | Low-temp. hot-pressing formed polyester composite material and its forming process of product |
| CN1858086A (en) * | 2006-06-07 | 2006-11-08 | 李刚 | Compounding process for DMC low shrinking polyester reinforced moulding material |
| CN1944530A (en) * | 2006-09-30 | 2007-04-11 | 李刚 | Low shrinking unsaturated polyester resin glass fibre reinforced mould plastic and its use |
| CN101157795A (en) * | 2007-09-30 | 2008-04-09 | 潘锦荣 | Resin mixture and glass reinforced plastic section bar prepared thereby |
-
2009
- 2009-02-11 CN CN2009100103558A patent/CN101508828B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997033942A1 (en) * | 1996-03-12 | 1997-09-18 | Nippon Shokubai Co., Ltd. | Unsaturated polyester resin composition and sheetlike molding material |
| EP0982327A1 (en) * | 1998-08-21 | 2000-03-01 | Sartomer Company Inc. | Unsaturated polyester resin compositions comprising metallic monomers |
| CN1367202A (en) * | 2002-02-10 | 2002-09-04 | 颜科 | Low-temp. hot-pressing formed polyester composite material and its forming process of product |
| CN1858086A (en) * | 2006-06-07 | 2006-11-08 | 李刚 | Compounding process for DMC low shrinking polyester reinforced moulding material |
| CN1944530A (en) * | 2006-09-30 | 2007-04-11 | 李刚 | Low shrinking unsaturated polyester resin glass fibre reinforced mould plastic and its use |
| CN101157795A (en) * | 2007-09-30 | 2008-04-09 | 潘锦荣 | Resin mixture and glass reinforced plastic section bar prepared thereby |
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