CN101191010B - Fibre enhancement modifying method for polyurethane foam plastic - Google Patents
Fibre enhancement modifying method for polyurethane foam plastic Download PDFInfo
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- CN101191010B CN101191010B CN2006101282439A CN200610128243A CN101191010B CN 101191010 B CN101191010 B CN 101191010B CN 2006101282439 A CN2006101282439 A CN 2006101282439A CN 200610128243 A CN200610128243 A CN 200610128243A CN 101191010 B CN101191010 B CN 101191010B
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Abstract
The invention relates to a fiber reinforced and modified method of a polyurethane foam plastic. The formula of raw materials added into raw materials of the polyurethane foam plastic is: 80-90 portions of polyether polyol 1; 10-20 portions of polyether polyol 2; 0.01-0.03 portions of catalyst; 0.5-2 portions of hard foam silicon oil; 0.2-0.5 portions of foaming agent; 5-20 portions of flame retardant; 0.1-0.2 portions of antioxidant; 115-150 portions of isocyanate; 230-300 portions of reinforcing materials. Compression molding forming is that: each component in the formula after mixed evenly is fast sprayed on the surface of reinforcing fiber, which is dipped uniformly and then put into the die for curing molding under room temperature; pulling and extruding molding is carried out through a pulling and extruding device; each component in the formula after mixed evenly is fast sprayed on the surface of the reinforcing fiber running with certain speed, which is dipped uniformly and then put into a die cavity for foaming, curing and molding.
Description
Technical field:
The invention belongs to technical field of polymer materials, a kind of fibre enhancement modifying method of urethane foam.
Background technology:
Urethane foam is a kind of widely used engineering materials, and it is low to have relative density, and specific modulus, specific tenacity height, and thermal insulation, sound insulation, resistance to chemical corrosion preferably are subjected to the generally attention of engineering circle.As a kind of ideal lightweight structural material, it is widely used in aspects such as aerospace component, navigation structural part and athletic sports appliance; As a kind of good energy absorbing material, it is through being commonly used for various crashproof buffering packages or cushioning material etc., but because urethane foam intensity is lower, under many special working conditions, do not reach service requirements, so a lot of research workers have carried out the research to the urethane foam enhancing modified, from the reinforcing filler developing history, glass fibre is the main research object that strengthens polyurethane system always, and normally adopt short glass fiber to strengthen polyurethane foam, as " polymer material science and engineering " calendar year 2001 the 17th volume the 3rd interim, different lengths such as Wang Jianhua: comprise 3mm, 6mm, 9mm, the short glass fiber of 12mm strengthens polyurethane foam, discovery is along with the increase of staple length, and foamy modulus of compression and compressive strength are and increase progressively trend; " Chemical Manufacture and technology " 2002 the 9th volume the 1st is interim, and Wang Wei's power is 195kg/m with 5%, 10%, 15% 3mm long glass fibres enhancing density respectively
3Polyurethane foam, the modulus of compression of the foam materials that obtains is increased to 55.2MPa, 59.9MPa, 69.3MPa successively by the 44.8MPa of pure foam; " matrix material journal " 2005 the 22nd volumes the 5th are interim, people such as Lu Zixing are by stress-strain curve static, that the dynamic compression experiment has obtained glass fiber reinforced polyester ammonia ester foamed plastic, find that glass fibre has not only improved the Young's modulus that strengthens porous plastics, has also improved the intensity of material.This shows that it is obvious that short glass fiber strengthens the polyurethane foam effect, but utilize the continuous fibre enhancement polyurethane porous plastics, domesticly do not appear in the newspapers as yet.
Summary of the invention:
In order to strengthen the intensity of urethane foam, the fibre enhancement modifying method that the purpose of this invention is to provide a kind of urethane foam, utilize the preparation of continuous fibre,, make it can substitute timber to strengthen the urethane foam over-all properties, the material that is obtained is widely used in technical fields such as warship cabin door, dividing plate, railroad tie, lorry compartment and civil construction material, the resulting product light weight, stable performance, the interface is even, good mechanical performance, erosion resistance is good.
In order to realize the foregoing invention purpose, the present invention adopts following technical scheme:
The fibre enhancement modifying method of described urethane foam, its formula for raw stock: with mass fraction %:
Polyether glycol 1 80～90
Polyether glycol 2 10～20
Catalyzer 0.01～0.03
Silicone oil 0.5～2 hard bubbles
Whipping agent 0.2～0.5
Fire retardant 5～20
Anti-aging agent 0.1～0.2
Isocyanic ester 115～150
Strongthener 230～300
The fiber-reinforced modified making moulding process of described urethane foam, the processing method of employing compression molding or pultrusion:
1, compression molding is after each component in the prescription is mixed, to be sprayed on the fortifying fibre surface with fast speeds, and dipping is evenly put into mould self-vulcanizing moulding;
2, pultrusion is to utilize extruding equipment to carry out, and after each component in the prescription is mixed, is sprayed on the fortifying fibre surface of moving with certain speed with fast speeds, enters die cavity foaming, curing, moulding after dipping is even.
Owing to adopt technical scheme as mentioned above, the present invention to be dependent on following proportioning principle, produce following positively effect:
Used polyether glycol is the main reaction raw material of preparation polyurethane foam in the prescription, polyether glycol should satisfy hydroxyl value 400～700mgKOH/g, functional group is between 4～8, but because the high polyether glycol of functionality, viscosity is bigger, relatively poor with the mutual solubility of other material, and the foams fragility that makes is big, therefore needs to adopt admixtured polyether.The present invention selects the series product of high functionality and low functionality polyether glycol for use, and as test raw material, the ratio of the two remains on 80～90: between 20～10 as 4110 series, 3031 series.
Isocyanic ester is the another kind of main reaction raw material of preparation polyurethane foam, commonly used have many phenyl polymethine polyisocyanates, rough tolylene diisocyanate and a refined toluene vulcabond, can select 5005 for use, M-200, PM-200 test, the TDI index is controlled between 110～130.
Polyurethane foam is in moulding process, catalyzer is a very important factor, and the choose reasonable catalyzer is the main contents of research, and catalyzer commonly used has two classes, be tertiary amines and organic tin, wherein the reaction of organic tin compound between catalyzing N CO-OH is than catalyzing N CO-H
2Reaction between the O is much better than, gel time is short, and tertiary amines is just in time opposite, in order to increase rising the time of sending out of resin, the selection tertiary amine compounds is proper, select for use aminated compoundss such as triethylamine, trolamine, triethylene diamine as catalyzer in the test, the amount of catalyzer is 0.01～0.03 part of polyether glycol total amount.
In the foaming process of polyurethane foam, suds-stabilizing agent can change the surface tension of system, improves the Combination of raw material, and can regulate cell size and structure, select the organosilicon stablizer that is fit to rigid foam in the test for use, make that the goods abscess is even, functional.
The whipping agent of hard polyurethane foams, commonly used have chlorinated and fluorinated hydrocarbon compound and a carbonic acid gas, and wherein carbonic acid gas is that isocyanic ester and water react with generate.Consider from environmental angle and price factor, material source, select for use water can satisfy environmental requirement as whipping agent, economical and practical.Because contain a large amount of fortifying fibres in the foams of preparation, the partial reaction heat in can the absorption reaction process can not cause the heartburn phenomenon of foams.
For improving the flame resistivity of polyurethane foam, kind and consumption to fire retardant in the test are studied, and under the prerequisite that does not influence material property, can select the halogenated organic phosphoric acid ester for use is fire retardant, makes the oxygen index of material reach 26～28%.
Add tangible photostabilizer UV-9 of polyurethane foam anti-aging action effect and antioxidant 2246 in the test.
Strongthener also is the main raw material of preparation material of the present invention, and it is very big to the mechanical property influence of end article, and there is big price differential in the different varieties fortifying fibre.The strongthener of the common roving of E type as urethane foam selected in this test for use.
The present invention's continuous fibre enhancement polyurethane porous plastics, the resulting product light weight, stable performance, the interface is even, good mechanical performance, erosion resistance is good, in certain field, can be used as the substitute products of timber.
Its performance index:
Embodiment one:
Polyether glycol 1 80, polyether glycol 2 20, catalyzer 0.01, the silicone oil 1 that hard bubbles, whipping agent 0.35, fire retardant 5, anti-aging agent 0.1, isocyanic ester 120, strongthener 230, the technology of employing compression molding or pultrusion:
1, compression molding is after each component in the prescription is mixed, to be sprayed on the fortifying fibre surface with fast speeds, and dipping is evenly put into mould self-vulcanizing moulding;
2, pultrusion is to utilize extruding equipment to carry out, and after each component in the prescription is mixed, is sprayed on the fortifying fibre surface of moving with certain speed with fast speeds, enters die cavity foaming, curing, moulding after dipping is even.
Embodiment two:
Polyether glycol 1 85, polyether glycol 2 15, catalyzer 0.01, the silicone oil 1 that hard bubbles, whipping agent 0.30, fire retardant 10, anti-aging agent 0.1, isocyanic ester 130, strongthener 240, the method for employing compression molding or pultrusion, concrete grammar is:
1, compression molding is after each component in the prescription is mixed, to be sprayed on the fortifying fibre surface with fast speeds, and dipping is evenly put into mould self-vulcanizing moulding;
2, pultrusion is to utilize extruding equipment to carry out, and after each component in the prescription is mixed, is sprayed on the fortifying fibre surface of moving with certain speed with fast speeds, enters die cavity foaming, curing, moulding after dipping is even.
Embodiment three:
Polyether glycol 1 90, polyether glycol 2 10, catalyzer 0.01, the silicone oil 1.5 that hard bubbles, whipping agent 0.25, fire retardant 15, anti-aging agent 0.1, isocyanic ester 150, strongthener 265, the method for employing compression molding or pultrusion, concrete grammar is:
1, compression molding is after each component in the prescription is mixed, to be sprayed on the fortifying fibre surface with fast speeds, and dipping is evenly put into mould self-vulcanizing moulding;
2, pultrusion is to utilize extruding equipment to carry out, and after each component in the prescription is mixed, is sprayed on the fortifying fibre surface of moving with certain speed with fast speeds, enters die cavity foaming, curing, moulding after dipping is even.
Claims (1)
1. the fibre enhancement modifying method of a urethane foam, it is characterized in that: its polyurethane foam is moulded
The composition of raw materials that material adds in the starting material: with mass fraction:
4110 serial polyether glycols 80～90
3031 serial polyether glycols 10～20
Catalyzer 0.01～0.03
Silicone oil 0.5～2 hard bubbles
Whipping agent 0.2～0.5
Fire retardant 5～20
Anti-aging agent 0.1～0.2
Isocyanic ester 115～150
Fortifying fibre 230～300
It makes moulding process, adopts the processing method of compression molding or pultrusion:
1), compression molding is after removing each component of fortifying fibre in will prescription and mixing, to be sprayed on the fortifying fibre surface with fast speeds, dipping is evenly put into mould self-vulcanizing moulding;
2), pultrusion is to utilize extruding equipment to carry out, and after each component of removing fortifying fibre in the prescription is mixed, is sprayed on fortifying fibre surface with the certain speed operation with fast speeds, dipping enters die cavity foaming, curing, moulding after evenly.
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| CN2006101282439A CN101191010B (en) | 2006-11-20 | 2006-11-20 | Fibre enhancement modifying method for polyurethane foam plastic |
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| CN2006101282439A CN101191010B (en) | 2006-11-20 | 2006-11-20 | Fibre enhancement modifying method for polyurethane foam plastic |
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| CN101191010A CN101191010A (en) | 2008-06-04 |
| CN101191010B true CN101191010B (en) | 2011-06-15 |
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Cited By (1)
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| WO2018033042A1 (en) * | 2016-08-17 | 2018-02-22 | 中国铁道科学研究院铁道建筑研究所 | High-fiber-content fiber-reinforced rigid polyurethane foam composite panel and method for manufacturing same |
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| CN101961933A (en) * | 2010-09-02 | 2011-02-02 | 北京立高科技股份有限公司 | Insulation waterproof coating and construction process thereof |
| CN102080490A (en) * | 2010-12-25 | 2011-06-01 | 欧创塑料建材(浙江)有限公司 | Polyurethane composite material energy-saving window frame or door leaf frame or door profile or door sheet |
| JP2013043374A (en) * | 2011-08-24 | 2013-03-04 | Nakagawa Sangyo Kk | Manufacturing method of interior substrate for automobile |
| CN103568337B (en) * | 2012-07-25 | 2016-01-13 | 株洲柳龙复合新材有限公司 | The preparation method of contact moudling polyurethane or polyurea composite material member |
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| CN105732934A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Preparation method of reinforced flame-retardant polyurethane composite material |
| CN106700031A (en) * | 2017-01-06 | 2017-05-24 | 沧州大化股份有限公司 | Treatment method of crude TDI |
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| CN1204346A (en) * | 1995-12-11 | 1999-01-06 | 巴斯福股份公司 | Process for preparing self-releasing, compact or cellular moulded bodies optionally containing reinforcing agents and made of polyisocyanate polyaddition products and internal mould release agents |
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| WO2018033042A1 (en) * | 2016-08-17 | 2018-02-22 | 中国铁道科学研究院铁道建筑研究所 | High-fiber-content fiber-reinforced rigid polyurethane foam composite panel and method for manufacturing same |
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| CN101191010A (en) | 2008-06-04 |
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Application publication date: 20080604 Assignee: Luoyang Sunrui Wind Turbine Blade.Ltd Assignor: No.725 Inst. China Shipping Heavy Industry Group Corp. Contract record no.: 2013410000025 Denomination of invention: Fibre enhancement modifying method for polyurethane foam plastic Granted publication date: 20110615 License type: Exclusive License Record date: 20130329 |
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