CN101113230A - Method for preparing unsaturated polyester cross-linking waste mold plastic - Google Patents

Method for preparing unsaturated polyester cross-linking waste mold plastic Download PDF

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Publication number
CN101113230A
CN101113230A CNA200710029602XA CN200710029602A CN101113230A CN 101113230 A CN101113230 A CN 101113230A CN A200710029602X A CNA200710029602X A CN A200710029602XA CN 200710029602 A CN200710029602 A CN 200710029602A CN 101113230 A CN101113230 A CN 101113230A
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China
Prior art keywords
unsaturated polyester
resin
waste
powder
linking
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Granted
Application number
CNA200710029602XA
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Chinese (zh)
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CN101113230B (en
Inventor
杜明亮
郭宝春
贾德民
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN200710029602XA priority Critical patent/CN101113230B/en
Publication of CN101113230A publication Critical patent/CN101113230A/en
Application granted granted Critical
Publication of CN101113230B publication Critical patent/CN101113230B/en
Expired - Fee Related legal-status Critical Current
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Abstract

The invention relates to a method to prepare moulding plastic from unsaturated polyester crosslinked waste, which comprises the steps: (1) the unsaturated polyester crosslinked waste such as glass fiber reinforced plastic, button plastic, etc. are put into a crushing machine to be crushed into 30 to 200 meshes; (2) the powder of unsaturated polyester crosslinked waste, suitable resin and auxilliary materials are mixed in a suitable scattering equipment such as a kneader to equally scatter the unsaturated polyester crosslinked waste powder and resin and assistant materials, wherein, the powder of unsaturated polyester crosslinked waste accounts for 60-95 percent of the total mass; (3) the mixture got form the step (2) is molded in a polymer moulding equipment such as a platens press in order to produce moulding plastic with unsaturated polyester crosslinked waste contents.

Description

The preparation method of unsaturated polyester cross-linking waste mold plastic
Technical field
The present invention relates to environment and material technology field, specifically is the preparation method of unsaturated polyester cross-linking waste mold plastic.
Background technology
The saturated polyester cross-linking waste mainly comes from following two aspects at present, and the one, glass fiber reinforced plastics product, the another one aspect is to be the artworks such as unsaturated polyester of representative with the button waste material.With glass reinforced plastic, button and artwork cross-linking waste is the unsaturated polyester cross-linking polymkeric substance of representative, the chemically crosslinked network structure of himself has caused its infusible characteristic, the same with rubber with crosslinking structure, remain one of material of the most difficult recycling at present.How environmental protection, economy, effectively reclaiming and this type of waste of recycle, is the focal issue that the whole society pays close attention to all the time.
About the processing of thermosetting resin waste, main now the employing buried method, combustion method and cracking process etc.Decompose because thermosetting resin is extremely difficult, therefore the method for burying had both been wasted land resources, also waste of manpower, material resources and financial resources; The burning rule has greatly been polluted atmospheric environment, and environment has been caused severe contamination; The cracking technique added value of traditional waste and old unsaturated polyester is low, and burning produces benzene He dioxin carcinogenic toxic gas and sewage such as (Dioxins) constitutes threat greatly to the mankind and ecology, prohibites in a lot of developed countries at present.Simultaneously, oil is a kind of limited, non-renewable strategic resource, thisly buries, burning or cracked method in fact also be a kind of great waste for petroleum resources.
Summary of the invention
In order to overcome above-mentioned shortcoming, the invention provides the preparation method of unsaturated polyester cross-linking waste mold plastic.This method is utilized traditional polymer shaping equipment, has the advantage simple, that cost is low, by adding low-cost, the high performance moulding compound of a spot of resin and subsidiary material preparation.
The preparation method of unsaturated polyester cross-linking waste mold plastic of the present invention comprises the steps:
Earlier unsaturated polyester cross-linking waste is crushed to 30~200 orders with pulverizer, again the unsaturated polyester cross-linking waste powder is mixed with dispersing apparatus with resin and subsidiary material, make unsaturated polyester cross-linking waste powder and resin and subsidiary material homodisperse, with platen-press mixture is carried out moulding at last, make moulding compound with high unsaturated polyester cross-linking waste content.
The mass percent 5~40% of resin of the present invention and subsidiary material, unsaturated polyester cross-linking waste powder are 60~95%.
Described resin comprises Resins, epoxy (EP), unsaturated polyester resin (UP), allylic resin, aminoresin, thermoset polyimide resin, cyanate ester resin, bimaleimide resin (BMIs), resol, urethane (PU), one or more mixtures of vinyl ester resin.
Described subsidiary material comprise one or more in resin solidification system and strongthener, toughening material and the packing material, and wherein the resin solidification system is solidifying agent and the promotor corresponding with used resin; Strongthener is meant one or more in glass fibre, carbon fiber, aramid fiber, superhigh molecular weight polyethylene fibers, nylon fiber and the trevira; Toughening material is meant one or more in natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, urethanes, paracril and the vulcanized rubber powder (for example tire glue powder); Packing material is meant one or more in lime carbonate, talcum powder, mica, kaolin, polynite, barium sulfate, silicon-dioxide, titanium dioxide, aluminum oxide, magnesium oxide, aluminium hydroxide, magnesium hydroxide, the graphite.
Described dispersing apparatus is meant one or more in shredder, mill, Banbury mixer, the kneader.
Know-why of the present invention is the unsaturated polyester die plastic that the unsaturated polyester cross-linking waste powder is directly had high-performance, low cost and extensive use by the mould pressing process moulding.Low amounts of resin is added in the unsaturated polyester cross-linking waste powder, can in the process of compression molding, form cross-linked network, and just there is crosslinking structure in unsaturated polyester cross-linking waste powder itself, therefore in matrix material, formed the interpenetrating(polymer)networks of resin and unsaturated polyester cross-linking waste, thereby resulting unsaturated polyester cross-linking waste mold plastic has higher mechanical property.
About resin and corresponding curing system thereof is prior art, and common textbook all has introduction, so the application does not elaborate.
The unsaturated polyester cross-linking waste mold plastic of the present invention's preparation can be widely used in making fields such as button, artwork, low-voltage apparatus, has broad application prospects.
The present invention compares with conventional process cross-linking waste method, has following advantage and beneficial effect:
1, unsaturated polyester cross-linking waste content therefore can very effective recovery and recycle unsaturated polyester resource greater than 60% quality in the moulding compound.
2, present method does not produce industrial sewage and waste gas, and environment is not polluted.
3, the unsaturated polyester cross-linking waste powder is with low cost, aboundresources, and prepared moulding compound has higher mechanical property, therefore has high added value.
4, the molding device that is adopted is the general-purpose equipment of forming polymer, thereby is easy to industrialization.
Embodiment
Embodiment 1
600 gram 30 purpose unsaturated polyester powder and 300 gram urethane resins, 35 are restrained 1, and 4-butyleneglycol (curing system), 5 gram dibutyl tin laurates (curing system) and 60 gram short glass fibers mix with kneader,
At 120 ℃, 15MPa with platen-press mold pressing moulding in 8 minutes, makes unsaturated polyester cross-linking waste mold plastic down again.The mechanical property of resulting moulding compound is as shown in table 1.
Embodiment 2
800 gram 100 purpose unsaturated polyester powder and 100 gram Resins, epoxy, 9 gram Dyhard RU 100s (curing system), 1 gram glyoxal ethyline (curing system), 50 gram short glass fibers and 40 gram tire glue powders are mixed with kneader, again with mixture at 160 ℃, 10MPa with platen-press mold pressing moulding in 6 minutes, makes unsaturated polyester cross-linking waste mold plastic down.The mechanical property of resulting moulding compound is as shown in table 1.
Embodiment 3
700 gram 200 purpose unsaturated polyester powder and 200 gram lacquer resinss, 10 gram hexamethylenetetramines (curing system), 50 gram short glass fibers, 40 gram powder talcum powder are mixed with mill, again with mixture at 150 ℃, 15MPa with platen-press mold pressing moulding in 7 minutes, makes unsaturated polyester cross-linking waste mold plastic down.The mechanical property of resulting moulding compound is as shown in table 1.
Embodiment 4
The unsaturated polyester powder and 50 of 950 grams, 100 order long time without surface modification are restrained unsaturated polyester resins and curing system mixes with kneader, use 180 ℃ of vulcanizing press again, mold pressing moulding in 5 minutes makes unsaturated polyester cross-linking waste mold plastic under the 25MPa.The mechanical property of resulting moulding compound is as shown in table 1.
Table 1
The resin kind Shock strength (KJ/m 2) Tensile strength (MPa) Modulus in flexure (GPa) Flexural strength (MPa)
Polyurethane-epoxy resin resol unsaturated polyester 5.61 3.97 4.02 3.12 82 93 89 67 3.23 3.78 4.06 4.53 83 117 123 95
Table 1 is the result show, the unsaturated polyester waste material moulding compound that contains the different resins kind of the present invention all has excellent mechanical performances.

Claims (9)

1. the preparation method of a unsaturated polyester cross-linking waste mold plastic is characterized in that may further comprise the steps:
(1) unsaturated polyester cross-linking waste is crushed to 30~200 orders with pulverizer;
(2) the waste powder that step (1) is obtained mixes with dispersing apparatus with resin and subsidiary material, and wherein the waste powder accounts for 60~95% quality of mixture;
(3) with dull and stereotyped compression polymer compression molding device the mixture of step (2) is carried out moulding, make unsaturated polyester cross-linking waste mold plastic.
2. method according to claim 1 is characterized in that described resin comprises one or more mixtures in Resins, epoxy, unsaturated polyester resin, allylic resin, aminoresin, thermoset polyimide resin, cyanate ester resin, bimaleimide resin, resol, urethane, the vinyl ester resin.
3. method according to claim 1 and 2, it is characterized in that described subsidiary material comprise one or more in resin solidification system, strongthener, toughening material, the packing material, wherein the resin solidification system comprises the solidifying agent corresponding with used resin or solidifying agent and accelerator mixture.
4. method according to claim 3 is characterized in that described strongthener adopts one or more in short glass fiber, carbon fiber, aramid fiber, superhigh molecular weight polyethylene fibers, nylon fiber, the trevira.
5. method according to claim 3 is characterized in that described toughening material adopts one or more mixtures in natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, urethanes, paracril, the vulcanized rubber powder.
6. method according to claim 3 is characterized in that described packing material adopts one or more in lime carbonate, talcum powder, mica, kaolin, polynite, barium sulfate, silicon-dioxide, titanium dioxide, aluminum oxide, magnesium oxide, aluminium hydroxide, magnesium hydroxide, the graphite.
7. method according to claim 1 is characterized in that described dispersing apparatus adopts shredder, mill, Banbury mixer or kneader.
8. method according to claim 1 is characterized in that described polymer in-mold press forming device comprises platen-press or vulcanizing press.
9. method according to claim 1 is characterized in that described compression molding is at 120 ℃~180 ℃, and 10-25MPa is down with platen-press mold pressing 5~8 minutes.
CN200710029602XA 2007-08-08 2007-08-08 Method for preparing unsaturated polyester cross-linking waste mold plastic Expired - Fee Related CN101113230B (en)

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CN102276999A (en) * 2011-07-26 2011-12-14 山东康境环保科技发展有限公司 Disposable plant fiber degradable tableware
CN101376718B (en) * 2008-08-13 2012-07-25 刘建平 Method for recycling waste polyurethane
EP2562206A1 (en) * 2011-08-23 2013-02-27 SGL Carbon SE Process for making a form from carbon fibers reinforced plastic by using a recycled carbon fibers reinforced plastic
CN102993665A (en) * 2012-08-22 2013-03-27 常熟市筑紫机械有限公司 Halogen-free unsaturated polyester glass reinforced plastic molding material
CN103035345A (en) * 2010-05-24 2013-04-10 南通市神马电力科技有限公司 Hollow composite insulator for 245KV and 252KV mutual inductors
CN103035344A (en) * 2010-05-24 2013-04-10 江苏神马电力股份有限公司 Hollow composite insulator for 170KV switch
CN103035346A (en) * 2010-05-24 2013-04-10 江苏神马电力股份有限公司 Hollow composite insulator for 363KV and 420KV switches
CN103035343A (en) * 2010-05-24 2013-04-10 江苏神马电力股份有限公司 Hollow composite insulator for 72.5KV and 100KV switches
CN103247396A (en) * 2010-05-24 2013-08-14 江苏神马电力股份有限公司 Hollow composite insulator for 126 KV, 145 KV and 170 KV mutual inductors
CN103254760A (en) * 2013-04-09 2013-08-21 刘庆芳 Bamboo charcoal-containing powder coating and its preparation method
CN103295703A (en) * 2010-05-24 2013-09-11 江苏神马电力股份有限公司 Hollow composite insulator for 245KV switch and 252KV switch
CN105175969A (en) * 2015-08-10 2015-12-23 南通德瑞森复合材料有限公司 Recycling method of old glass fiber reinforced plastics
CN106589840A (en) * 2017-02-07 2017-04-26 和县隆盛精密机械有限公司 High-strength wear-resistant material for mechanical arm and preparation method of high-strength wear-resistant material
CN106633737A (en) * 2016-12-01 2017-05-10 安徽星元环保科技有限公司 Glass reinforced plastic material for constructing low temperature resistant septic-tank
CN106751632A (en) * 2016-12-01 2017-05-31 安徽星元环保科技有限公司 A kind of fiberglass raw material for manufacturing oil interceptor
CN107903467A (en) * 2017-11-08 2018-04-13 四川塑金科技有限公司 Railway joints polymer composites made of waste plastic
CN107936336A (en) * 2017-11-08 2018-04-20 四川塑金科技有限公司 Regenerate the preparation method of railway joints
CN108841194A (en) * 2017-09-15 2018-11-20 广州简米餐具有限公司 Utilize the composite material and preparation method of biomass fiber and the preparation of imitative porcelain salvage material
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CN111234493A (en) * 2020-03-17 2020-06-05 河北润达环保科技有限公司 Functional plastic prepared from glass fiber reinforced plastic waste and production method and application thereof
CN111454585A (en) * 2020-03-09 2020-07-28 句容市久诺复合材料有限公司 High-heat-resistance insulating SMC composite material
CN111484726A (en) * 2020-05-22 2020-08-04 江苏爱特恩高分子材料有限公司 Preparation method of waste cable sheath modified polyurethane glass fiber reinforced plastic composite material
CN112175373A (en) * 2020-09-23 2021-01-05 广东智信电气有限公司 Unsaturated polyester glass fiber reinforced plastic and process steps
CN113652069A (en) * 2021-09-15 2021-11-16 浙江迈利达集团有限公司 Resin button waste regeneration button and preparation method thereof

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CN101376718B (en) * 2008-08-13 2012-07-25 刘建平 Method for recycling waste polyurethane
CN103035345A (en) * 2010-05-24 2013-04-10 南通市神马电力科技有限公司 Hollow composite insulator for 245KV and 252KV mutual inductors
CN103035344A (en) * 2010-05-24 2013-04-10 江苏神马电力股份有限公司 Hollow composite insulator for 170KV switch
CN103035346A (en) * 2010-05-24 2013-04-10 江苏神马电力股份有限公司 Hollow composite insulator for 363KV and 420KV switches
CN103035343A (en) * 2010-05-24 2013-04-10 江苏神马电力股份有限公司 Hollow composite insulator for 72.5KV and 100KV switches
CN103247396A (en) * 2010-05-24 2013-08-14 江苏神马电力股份有限公司 Hollow composite insulator for 126 KV, 145 KV and 170 KV mutual inductors
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