CN101831125A - Preparation method of acrylic resin-based glass fiber reinforced plastic - Google Patents

Preparation method of acrylic resin-based glass fiber reinforced plastic Download PDF

Info

Publication number
CN101831125A
CN101831125A CN 201010146568 CN201010146568A CN101831125A CN 101831125 A CN101831125 A CN 101831125A CN 201010146568 CN201010146568 CN 201010146568 CN 201010146568 A CN201010146568 A CN 201010146568A CN 101831125 A CN101831125 A CN 101831125A
Authority
CN
China
Prior art keywords
acrylic resin
glass fiber
reinforced plastic
fiber reinforced
based glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 201010146568
Other languages
Chinese (zh)
Other versions
CN101831125B (en
Inventor
刘国祥
杨德兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NANJING SPARE COMPOSITES CO Ltd
Original Assignee
NANJING SPARE COMPOSITES CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NANJING SPARE COMPOSITES CO Ltd filed Critical NANJING SPARE COMPOSITES CO Ltd
Priority to CN2010101465686A priority Critical patent/CN101831125B/en
Publication of CN101831125A publication Critical patent/CN101831125A/en
Application granted granted Critical
Publication of CN101831125B publication Critical patent/CN101831125B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a preparation method of acrylic resin-based glass fiber reinforced plastic, comprising the following steps of: pultruding 100 percent of acrylic resin, 150-200 percent of powdery aluminum hydroxide, 5-30 percent of carbon dust, 0.3-2.5 percent of benzoyl peroxide, 0.2-5 percent of polyethylene glycol and 0.5-6 percent of stearic acid or stearic acid salt by a pultrusion process; feeding the materials into a process tank; and continuously forming by using glass fiber yarn as a vector and a die for heating in three-section areas to obtain the acrylic resin-based glass fiber reinforced plastic. The acrylic resin-based glass fiber reinforced plastic has high combustion property and an oxygen index up to 70; in addition, after 150 parts of aluminum hydroxide and 5-30 parts of carbon dust are filled, the acrylic resin-based glass fiber reinforced plastic keeps high comprehensive mechanical properties, longitudinal stretching strength as high as 500MPa, longitudinal bending strength as high as 400MPa and elastic modulus up to 25.5GPa.

Description

A kind of preparation method of acrylic resin-based glass fiber reinforced plastic
Technical field
The present invention relates to a kind of resin-based glass fiber reinforced plastic and preparation method thereof.
Technical background
Plastics, rubber and chemical fibre three big synthetic material industry have obtained the development of prominent flying property, a lot
The field has replaced some goods of being made by traditional natural resources, chemical building material used in the picture building replaces a lot of traditional steel, and plastic working product and organic polymer polymeric material also are widely used in fields such as traffic, electrical equipment, communication in addition.But the inflammableness of these three big synthetic materialss has also been brought huge potential safety hazard to the whole society, becomes the social concern that receives much attention.So increase their flame retardant resistance, farthest reduce the important topic that its inflammable grade becomes the investigators of related scientific research institutes and enterprises and institutions.
For the essence of most of organic polymer materials, they are impossible make absolute fire prevention
Material, unique possible way is to reduce its burning grade as much as possible, slow down combustionvelocity, method at present commonly used is to add fire retardant in its goods, and common have boron flame retardant, halogenated flame retardant and aluminium hydroxide, this metalloid oxyhydroxide of magnesium hydroxide etc.Another common method is carried out chemical modification to the raw material organic high molecular polymer exactly, makes after its modification the flame retardant resistance of self bring up to a suitable degree.
For the glass filament reinforced plastics that the present invention relates to, wherein play the glass fibre material of enhancement
The right and wrong of material own are flammable, just carry this additive flame retardant of glass fibre with respect to single plastics glass filament reinforced plastics.Usually in glass filament reinforced plastics, add aluminium hydroxide, its flame retardant resistance is improved once more.That aluminium hydroxide has concurrently is fire-retardant, press down cigarette, fill three kinds of functions, and its consumption accounts for about 65% of additive flame retardant.Seeking aspect the glass filament reinforced plastics goods high flame retardant, investigators also selecting suitable flame retardant resin base as another the valid approach of adding outside the fire retardant, comprise and select modification or non-modified resins for use.
In sum, the flame retardant resistance method that improves resin-based glass fiber reinforced plastic has two kinds of approach: the one, select the resin of flame retardant resistance for use; The 2nd, select the fire retardant of addition type for use, simultaneously also as filler.Improve its flame retardant resistance and must possess following condition:
1, flaming combustion can be stoped, flameless combustion can be suppressed again;
2, additive flame retardant itself is nontoxic, the few cigarette of its pyrolysis and combustion product, low toxicity, non-stimulated and corrodibility.
3, fire retardant is not volatile, oozes out or moves, and is ageing-resistant and flame retardant resistance stable;
4, it is too big to guarantee that as the additive flame retardant of filler mechanical property to goods can not influence after interpolation, and can not influence its off-balancesheet and see.
Summary of the invention
The object of the invention has provided glass filament reinforced plastics of a kind of high flame retardant, high comprehensive mechanical property and preparation method thereof.Especially use additive flame retardant after interpolation, will guarantee the mechanical property of goods is unlikely to that big influence is arranged, do not influence its off-balancesheet and see, and be a kind of nontoxic combustion-proof glass fiber reinforced plastics as filler.
Technical solution of the present invention is: acrylic resin-based glass fiber reinforced plastic feed composition, content (amount of resin per-cent relatively) and pultrude process parameter:
(1) acrylic resin is 100%
(2) powdery aluminium hydroxide 150-200%
(3) carbon dust 5-30%
(4) benzoyl peroxide or with methylethyl ketone peroxide 0.3-2.5%
(5) polyoxyethylene glycol 0.2-5%
(6) hard ester acid or hard acid ester salt 0.5-6%;
With the pultrude process pultrusion, above-mentioned materials is entered in the technology hopper, as carrier, by continuously shaped, make product with glass fiber yarn through three sections regional heated die with following condition pultrusion:
(7) content of glass fiber 180-250%
(8) pultrusion die temperature I district 100-130 ℃; 110-140 ℃ in II district; 90-120 ℃ in III district
(9) pultrusion speed 0.1-0.7m/min
In the said components, consider that curing speed is unsuitable too fast, benzoyl peroxide and/or methylethyl ketone peroxide ratio should be and be respectively 0.1-1% and 0.3-2% for best.
The 0.2-5% polyoxyethylene glycol that adds in the said components is to use as dispersion agent, and purpose is to make that a high proportion of aluminium hydroxide is evenly distributed in the resin in the batching, and consumption is also unsuitable too many, can reduce the mechanical property of goods too much.
Hard ester acid or hard acid ester salt (Zinc Stearate) in the said components are a kind of lubricant releasing agents, purpose is to make goods reduce the frictional force of goods and mould behind the curing molding in mould, depanning smoothly under suitable tractive force, but can not be too many, the too many mechanical property that also can reduce goods, optimum quantity should be 0.5-6%.
Content of glass fiber in the said components should be 180-250%, and higher meeting makes the pultrusion resistance very excessive
To snap gauge; The goods mechanical property can reduce when on the low side, and phenomenon uneven even that come unstuck also can appear in the outward appearance of goods simultaneously.
Preparation process of the present invention is:
After earlier the carbon dust of the aluminium hydroxide of 100 parts of acrylic resins, 150-200 part and 5-30 part being mixed and stirring, add the polyoxyethylene glycol of 0.2-5 part again, the stirring that the Zinc Stearate of 0.5-6 part does not stop makes its uniform distribution, leaving standstill 30min makes it be cooled to room temperature, add benzoyl peroxide of 0.1-1 part and the methylethyl ketone peroxide of 0.3-2 part more successively, stir 5min once more.The batching that will mix is poured in the pultrusion hopper at last, under suitable tractive force, is carrier with the glass fibre of 180-250 part, with the pultrusion speed of 0.1-0.7m/min by mould molding through above-mentioned three sections Heating temperatures.
The invention has the beneficial effects as follows: have following several big advantage with respect to existing flame retardant type glass filament reinforced plastics: the resin base of 1, selecting for use is polyurethane-modified acrylic resin, possesses flame retardant resistance and not halogen-containing, few cigarette during burning; 2, the aluminium hydroxide of selecting for use has the function of fire retardant and filler simultaneously concurrently, and itself nontoxic, non-stimulated and corrodibility; 3, the product flame retardant rating height for preparing, oxygen index is up to 70; Few cigarette during burning, the smoke density grade is 15; 4, adding after relative resin quality per-cent is the aluminium hydroxide of 150-200%, can keep high comprehensive mechanical property, longitudinal tensile strength up to 500MPa, buckling strength reach 400MPa, shock strength reaches 300KJ/m 2Young's modulus reaches 25.5GPa.
Specific embodiment
The polyurethane modified acrylic resin based glass fiber reinforced plastic is prepared into the glass filament reinforced plastics (GFRP) of high flame retardant, high comprehensive mechanical property.The feed composition of described GFRP, content (the 1212 weight resin per-cents that adopt relatively) and pultrude process parameter are as follows:
Form example ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 ??9 ??10
Acrylic resin ??1 ??1 ??1 ??1 ??1 ??1 ??1 ??1 ??1 ??1
Powdery aluminium hydroxide ??1.6 ??1.5 ??1.7 ??1.8 ??2 ??2 ??2 ??1.5 ??2 ??2
Carbon dust ??0.1 ??0.2 ??0.3 ??0.2 ??0.3 ??0.05 ??0.05 ??0.05 ??0.1 ??0.2
Benzoyl peroxide ??0.01 ??0.01 ??0.001 ??0.01 ??0.005 ??0.01
Methylethyl ketone peroxide ??0.01 ??0.01 ??0.01 ??0.02 ??0.01 ??0.01 ??0.003
Polyoxyethylene glycol ??0.02 ??0.01 ??0.05 ??0.03 ??0.01 ??0.01 ??0.02 ??0.01 ??0.03 ??0.002
Zinc Stearate ??0.01 ??0.03 ??0.04 ??0.01 ??0.03 ??0.04 ??0.06 ??0.01 ??0.02 ??0.005
Glass fibre ??1.8 ??2 ??2.5 ??2.2 ??1.9 ??2.3 ??2 ??3 ??2.1 ??2
Zinc Stearate can adopt hard ester acid or calcium stearate etc. to there is no remarkable difference.
1, pultrusion die temperature I district is 110 ℃; 110 ℃ in II district; 100 ℃ in III district all can, pultrusion speed is especially at 0.25m/min;
2, I district, II district, III district can also be a kind of embodiment at 110-120 ℃ all, and pultrusion speed is especially at 0.5m/min;
3, pultrusion die temperature I district 105-110 ℃; 130-140 ℃ in II district; The III district is another kind of embodiment for 95-100 ℃, and pultrusion speed is especially at 0.25-0.55m/min;
4, pultrusion die temperature: 110 ℃ in I district; 120 ℃ in II district; 105 ℃ in III district all can reach good effect.
Preparation method: the polyurethane modified acrylic resin 1212 of 50kg (100%) is packed in the agitation vat, branch takes by weighing powdery aluminium hydroxide and the carbon dust of 85kg and 7.5kg in addition and pours in the agitation vat, after stirring, the polyoxyethylene glycol and the stearic acid zinc powder that take by weighing 250g and 750g are more respectively poured wherein stirring into, approximately stop behind the 5min stirring, leave standstill and make it be cooled to room temperature about 30min, take by weighing 150g benzoyl peroxide, 450g methylethyl ketone peroxide at last in wherein, stop after continuing to stir about 5min, deliver to immediately in the pultrude process hopper.Under suitable tractive force, with the glass fiber yarn of the 4800tex of 100kg as carrier, with the pultrusion speed of 0.25m/min by through heating (110 ℃ in I districts, three sections zones; 120 ℃ in II district; 105 ℃ in III district) mould is continuously shaped, makes product.
The every performance of product sees Table one (to form the prescription of example 9), processing condition: 110 ℃ in pultrusion die temperature I district; 110 ℃ in II district; 100 ℃ in III district all can, pultrusion speed is especially at 0.25m/min.
The every performance index of table one product
Figure GSA00000079481300041
The acrylic resin of other trades mark, relatively cross a kind of Halogen resin trade mark: XF-9011 is the resin that belongs to flame retardant resistance equally.The Halogen resin, the trade mark: XF-9011 producer: DSM (Nanjing DSM).The trade mark of typical polyurethane modified acrylic resin: 1212 producers: Scott Bader (Si Gaote Ahmedabad), these two kinds relatively is that the flame retardant resistance and the comprehensive mechanical property of polyurethane modified acrylic resin is all good.

Claims (6)

1. preparation method of acrylic resin-based glass fiber reinforced plastic, when the pultrude process parameter is as follows to it is characterized in that the weight percent of the relative acrylic resin amount of feed composition, content of described GFRP:
(1) acrylic resin 100%
(2) powdery aluminium hydroxide 150-200%
(3) carbon dust 5-30%
(4) benzoyl peroxide or with methylethyl ketone peroxide 0.3-2.5%
(5) polyoxyethylene glycol 0.2-5%
(6) hard ester acid or hard acid ester salt 0.5-6%
And with the pultrude process pultrusion, above-mentioned materials is entered in the technology hopper, as carrier, by continuously shaped, makes product through three sections regional heated die with following condition pultrusion with glass fiber yarn:
(7) content of glass fiber 180-250%
(8) pultrusion die temperature I district 100-130 ℃; 110-140 ℃ in II district; 90-120 ℃ in III district
(9) pultrusion speed 0.1-0.7m/min.
2. preparation method of acrylic resin-based glass fiber reinforced plastic according to claim 1 is characterized in that described aluminium hydroxide is powdery, and specific surface area (BET) is 4m 2More than/the g.
3. preparation method of acrylic resin-based glass fiber reinforced plastic according to claim 1 it is characterized in that described benzoyl peroxide contains two benzoyls, and consumption is 0.1-1% with respect to the acrylic resin mass percent.
4. preparation method of acrylic resin-based glass fiber reinforced plastic according to claim 1 is characterized in that the consumption of described methylethyl ketone peroxide is 0.3-2% with respect to 1212 resin quality per-cents.
5. preparation method of acrylic resin-based glass fiber reinforced plastic according to claim 1 is characterized in that the relative acrylic resin mass percent of described Zinc Stearate is 0.5-6%.
6. preparation method of acrylic resin-based glass fiber reinforced plastic according to claim 1, it is characterized in that being undertaken: after earlier the carbon dust of the aluminium hydroxide of 100 parts by weight of acrylic acid resins, 150-200 part and 5-30 part being mixed and stirring by following step, add the polyoxyethylene glycol of 0.2-5 part again, the stirring that the Zinc Stearate of 0.5-6 part does not stop makes its uniform distribution, leaving standstill 30min makes it be cooled to room temperature, add benzoyl peroxide of 0.1-1 part and the methylethyl ketone peroxide of 0.3-2 part more successively, stir 5min; The batching that will mix is poured in the pultrusion hopper at last, under suitable tractive force, is carrier with the glass fibre of 180-250 part, with the pultrusion speed of 0.1-0.7m/min by through three sections heated die moulding.
CN2010101465686A 2010-04-14 2010-04-14 Preparation method of acrylic resin-based glass fiber reinforced plastic Expired - Fee Related CN101831125B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010101465686A CN101831125B (en) 2010-04-14 2010-04-14 Preparation method of acrylic resin-based glass fiber reinforced plastic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010101465686A CN101831125B (en) 2010-04-14 2010-04-14 Preparation method of acrylic resin-based glass fiber reinforced plastic

Publications (2)

Publication Number Publication Date
CN101831125A true CN101831125A (en) 2010-09-15
CN101831125B CN101831125B (en) 2011-08-17

Family

ID=42715356

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010101465686A Expired - Fee Related CN101831125B (en) 2010-04-14 2010-04-14 Preparation method of acrylic resin-based glass fiber reinforced plastic

Country Status (1)

Country Link
CN (1) CN101831125B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103587541A (en) * 2013-10-21 2014-02-19 江苏恒神纤维材料有限公司 Outer cover of light maglev train cab and integrated forming process of outer cover
CN107696352A (en) * 2017-11-18 2018-02-16 蚌埠市华鼎机械科技有限公司 A kind of preparation method of fiber reinforced plastic mold
CN108756119A (en) * 2018-06-15 2018-11-06 新土木(大连)建筑设计院有限公司 A kind of plug-in systems of FRP applied to construction wall, preparation method and applications
JP2018536030A (en) * 2015-11-23 2018-12-06 ユナイテッド イニシエーターズ ゲーエムベーハー BCHPC with reduced burning rate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869178A (en) * 1994-08-25 1999-02-09 The University Of North Carolina At Chapel Hill Pultruded fiber-reinforced plastic and related apparatus and method
US5916509A (en) * 1997-02-07 1999-06-29 Durhman; Paul P. Actinic irradiation and curing of plastic composites within a material forming die
CN1560134A (en) * 2004-02-24 2005-01-05 天津市金锚科技发展有限公司 Preparing composite of modifing glass fiber reinforced plastics pultrusion section bar and preparation method thereof
CN1590452A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Composition of glass fiber reinforced thermoplastic polymer
WO2007065071A2 (en) * 2005-12-01 2007-06-07 Certain Teed Corporation Method and system for making an article reinforced with continuous filaments
CN101050296A (en) * 2007-04-20 2007-10-10 佛山市华联有机硅有限公司 Acrylic resin latex modified by fire retardation type organosilicon, and preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869178A (en) * 1994-08-25 1999-02-09 The University Of North Carolina At Chapel Hill Pultruded fiber-reinforced plastic and related apparatus and method
US5916509A (en) * 1997-02-07 1999-06-29 Durhman; Paul P. Actinic irradiation and curing of plastic composites within a material forming die
CN1590452A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Composition of glass fiber reinforced thermoplastic polymer
CN1560134A (en) * 2004-02-24 2005-01-05 天津市金锚科技发展有限公司 Preparing composite of modifing glass fiber reinforced plastics pultrusion section bar and preparation method thereof
WO2007065071A2 (en) * 2005-12-01 2007-06-07 Certain Teed Corporation Method and system for making an article reinforced with continuous filaments
CN101050296A (en) * 2007-04-20 2007-10-10 佛山市华联有机硅有限公司 Acrylic resin latex modified by fire retardation type organosilicon, and preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
《实用口腔医学杂志》 20010531 张文云等 "高强玻璃纤维/树脂复合材料的力学性能研究" 212-214 1-6 第17卷, 第3期 2 *
《纤维复合材料》 19890331 D.R.SAYERS "甲基丙烯酸酯基树脂在拉挤中的应用研究" 46-54 1-6 , 第1期 2 *
《纤维复合材料》 19890731 DAVID R.SAYERS "甲基丙烯酸酯基树脂在拉挤中应用的进一步进展" 55-60 1-6 , 第2期 2 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103587541A (en) * 2013-10-21 2014-02-19 江苏恒神纤维材料有限公司 Outer cover of light maglev train cab and integrated forming process of outer cover
CN103587541B (en) * 2013-10-21 2016-06-15 江苏恒神股份有限公司 Lightweight magnetically levitated train driver's cab outer housing and integral forming technique
JP2018536030A (en) * 2015-11-23 2018-12-06 ユナイテッド イニシエーターズ ゲーエムベーハー BCHPC with reduced burning rate
CN107696352A (en) * 2017-11-18 2018-02-16 蚌埠市华鼎机械科技有限公司 A kind of preparation method of fiber reinforced plastic mold
CN108756119A (en) * 2018-06-15 2018-11-06 新土木(大连)建筑设计院有限公司 A kind of plug-in systems of FRP applied to construction wall, preparation method and applications

Also Published As

Publication number Publication date
CN101831125B (en) 2011-08-17

Similar Documents

Publication Publication Date Title
CN102617915B (en) Anti-mildew halogen-free flame-retardant smoke-suppression wood-plastic composite material and preparation method thereof
CN103554626B (en) A kind of fretting map polyethylene based wood-plastic composite material and preparation method thereof
CN103113677B (en) Halogen-free flame-retardant anti-mildew composite and preparation method thereof
CN103013089B (en) Flame-retardant glass fiber reinforced PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof
CN101831125B (en) Preparation method of acrylic resin-based glass fiber reinforced plastic
CN102977624B (en) A kind of degradable type bamboo-plastic composite material with superhigh tenacity and preparation method thereof
CN108250566A (en) A kind of low warpage halogen-free expanded flame-retardant Long Glass Fiber Reinforced PP Composite and preparation method thereof
CN103059562B (en) High-glossiness anti-warping high-strength PA6 (polyamide 6) composite material, and preparation and application thereof
CN102850650A (en) Basalt fiber reinforced polypropylene composite material and preparation method thereof
CN102219993A (en) Low-cost halogen-free inflaming-retarding polyamide material for low-voltage apparatus housings
CN103788637B (en) A kind of composite and preparation method thereof
CN102731933A (en) Low shrinkage flame retardation PVC protective layer material used for indoor optical cable and its preparation method
CN103849142A (en) Lightweight flame retardant modified polyamide material and its preparation method
CN103160080B (en) A kind of halogen-free flame-retardant long fiber glass reinforced PBT composite and preparation method thereof
CN102690515A (en) Flame-retardant composite material with easy dyeing and laser marking and preparation method thereof
CN112592523A (en) Anti-static composite wood-plastic material and preparation method thereof
CN103709544A (en) High-strength micro-foaming PVC wood plastic special-purpose material and its preparation method and use
CN108676331A (en) A kind of high-strength high temperature-resistant PBT/PC alloy resin materials and preparation method thereof
CN103772880A (en) ABS/PET material for extrusion process and preparation method of ABS/PET material
CN104448554A (en) Highlight high-flexibility polypropylene environment-friendly flame retardant material and preparation method thereof
CN106317555B (en) A kind of high-density polyethylene resin and preparation method thereof, application
CN103224668B (en) A kind of polypropylene-base bamboo moulds the preparation method of foam composite material
CN105348641A (en) Calcium carbonate filled flame-retardant polypropylene material and preparation method thereof
CN111234369A (en) Wear-resistant polypropylene composite material and preparation method thereof
CN103772881A (en) Weather-proof flame retardant ABS/PET material for extrusion process and preparation method of ABS/PET material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110817

CF01 Termination of patent right due to non-payment of annual fee