CN105566892A - Modified carbon fiber/polyurethane composite material and preparation method thereof - Google Patents
Modified carbon fiber/polyurethane composite material and preparation method thereof Download PDFInfo
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- CN105566892A CN105566892A CN201610128326.1A CN201610128326A CN105566892A CN 105566892 A CN105566892 A CN 105566892A CN 201610128326 A CN201610128326 A CN 201610128326A CN 105566892 A CN105566892 A CN 105566892A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
Abstract
The invention discloses a modified carbon fiber/polyurethane composite material, which is prepared from the following components in parts by weight: a component A of 30 to 50 parts of polyester polyol, 30 to 50 parts of polyether polyol, 2 to 5 parts of carbon fibers, 4 to 8 parts of hollow glass micro-beads, 1 to 2 parts of cross-linking agent and 2 to 3 parts of stabilizing agent; a component B of 20 to 30 parts of isocyanate and 1.5 to 3 parts of polyolefin block copolymers (OBCs). The invention also discloses a preparation method of the composite material. The composite material is good in heat resistance, high temperature resistance and corrosion resistance, small in heat expansion coefficient and excellent in mechanical property; further, the preparation method is simple; technological conditions are mild; the cost is low.
Description
Technical field:
The present invention relates to field of compound material, be specifically related to a kind of modified carbon fiber/compound polyurethane material.
Background technology:
Polyurethane material is a kind of synthetic materials between rubber and plastics, there is the performance of a series of excellences such as high mechanical strength, unreactiveness, high abrasion, low-temperature performance, adhesive property and elasticity is good, but itself there is the shortcomings such as poor heat resistance, softening and heat decomposition temperature are low, along with the development of science and technology and the expansion of application, enhancing modified need be carried out to urethane, improve its performance.Therefore, the compound polyurethane material being devoted to develop Good Heat-resistance becomes the important topic of polyurethane field research.
Carbon fiber be a kind of carbon content higher than 90% inorganic polymer fiber, there is high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, antifatigue, creep resistance, a series of excellent properties such as thermal expansivity is little, utilize the excellent properties of carbon fiber, strongthener is it can be used as to join in spool elastomerics, mechanical property and the resistance toheat of matrix material can be significantly improved, but carbon fiber surface activity group is few, itself and polyurethane elastomer poor compatibility, the matrix material prepared is easy to cracking, therefore, modification need be carried out to carbon fiber/compound polyurethane material, could be realized it apply widely.
Summary of the invention:
The object of this invention is to provide a kind of modified carbon fiber/compound polyurethane material, its good heat resistance, high temperature resistant, good corrosion resistance, thermal expansivity is little, and mechanical property is excellent.
Another object of the present invention is to provide the preparation method of modified carbon fiber/compound polyurethane material.
For achieving the above object, the present invention is by the following technical solutions:
A kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 30-50 part, polyether glycol 30-50 part,
Carbon fiber 2-5 part, hollow glass micropearl 4-8 part,
Linking agent 1-2 part, stablizer 2-3 part;
B component:
Isocyanic ester 20-30 part,
Polyolefin block formula multipolymer OBCs1.5-3 part.
Preferred as technique scheme, a kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 45 parts, polyether glycol 30 parts,
2.5 parts, carbon fiber, hollow glass micropearl 5 parts,
Linking agent 2 parts, stablizer 2.5 parts;
B component:
Isocyanic ester 30 parts,
Polyolefin block formula multipolymer OBCs2 part.
Preferred as technique scheme, described polyester polyol is one or more mixing in poly-adipate glycol propylene glycol ester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol, polycarbonate polyol.
Preferred as technique scheme, described polyether glycol is one or more mixing in Amino Terminated polyether(ATPE) polyvalent alcohol, 6305 polyether glycols, low functionality polyether glycol.
Preferred as technique scheme, the diameter of described carbon fiber is 1-2 μm, and length is 5-10 μm.
Preferred as technique scheme, the size of described hollow glass micropearl is 20-30nm.
Preferred as technique scheme, described isocyanic ester is 4, one or more mixing in 4 '-diphenylmethanediisocyanate, isophorone diisocyanate.
Preferred as technique scheme, described linking agent is silane coupling agent.
A preparation method for modified carbon fiber/compound polyurethane material, comprises the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 80-100 DEG C, ultrasonic 1-2h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 100-120 DEG C, ultrasonic 1-2h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
Preferred as technique scheme, in step (1), described ultrasonic power is 1000W.
The present invention has following beneficial effect:
Polyolefin block formula multipolymer, effectively can improve snappiness and the shock resistance of matrix material, carbon fiber, hollow glass micropearl linking agent crosslinked under, can stable dispersion in the composite, thus greatly improving toughness and the intensity of material, the matrix material prepared is not easy to crack, and this composite material and preparation method thereof is simple, mild condition, cost is low.
Embodiment:
For a better understanding of the present invention, below by embodiment, the present invention is further described, and embodiment, only for explaining the present invention, can not form any restriction to the present invention.
Embodiment 1
A kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 30 parts, polyether glycol 30 parts,
2 parts, carbon fiber, hollow glass micropearl 4 parts,
Linking agent 1 part, stablizer 2 parts;
B component:
Isocyanic ester 20 parts,
Polyolefin block formula multipolymer OBCs1.5 part.
Its preparation method comprises the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 80 DEG C, ultrasonic 1h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 100 DEG C, ultrasonic 1h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
Embodiment 2
A kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 50 parts, polyether glycol 50 parts,
5 parts, carbon fiber, hollow glass micropearl 8 parts,
Linking agent 2 parts, stablizer 3 parts;
B component:
Isocyanic ester 30 parts,
Polyolefin block formula multipolymer OBCs3 part.
Its preparation method comprises the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 100 DEG C, ultrasonic 2h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 120 DEG C, ultrasonic 2h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
Embodiment 3
A kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 35 parts, polyether glycol 35 parts,
3 parts, carbon fiber, hollow glass micropearl 5 parts,
Linking agent 1.2 parts, stablizer 2.2 parts;
B component:
Isocyanic ester 22 parts,
Polyolefin block formula multipolymer OBCs1.8 part.
Its preparation method comprises the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 85 DEG C, ultrasonic 1.2h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 105 DEG C, ultrasonic 1.2h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
Embodiment 4
A kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 38 parts, polyether glycol 38 parts,
3.5 parts, carbon fiber, hollow glass micropearl 6 parts,
Linking agent 1.4 parts, stablizer 2.4 parts;
B component:
Isocyanic ester 24 parts,
Polyolefin block formula multipolymer OBCs2 part.
Its preparation method comprises the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 90 DEG C, ultrasonic 1.4h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 110 DEG C, ultrasonic 1.4h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
Embodiment 5
A kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 40 parts, polyether glycol 40 parts,
4 parts, carbon fiber, hollow glass micropearl 7 parts,
Linking agent 1.6 parts, stablizer 2.6 parts;
B component:
Isocyanic ester 26 parts,
Polyolefin block formula multipolymer OBCs2.5 part.
Its preparation method comprises the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 95 DEG C, ultrasonic 1.6h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 115 DEG C, ultrasonic 1.6h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
Embodiment 6
A kind of modified carbon fiber/compound polyurethane material, with parts by weight, comprises following component:
Component A:
Polyester polyol 45 parts, polyether glycol 45 parts,
4.5 parts, carbon fiber, hollow glass micropearl 7.5 parts,
Linking agent 1.8 parts, stablizer 2.8 parts;
B component:
Isocyanic ester 28 parts,
Polyolefin block formula multipolymer OBCs3 part.
Its preparation method comprises the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 100 DEG C, ultrasonic 1.8h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 120 DEG C, ultrasonic 1.8h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
Performance test is carried out to matrix material provided by the invention below.
Table 1
From table 1, modified carbon fiber/compound polyurethane material provided by the invention, has excellent shock resistance and higher specific tenacity.
Claims (10)
1. modified carbon fiber/compound polyurethane material, is characterized in that, with parts by weight, comprises following component:
Component A:
Polyester polyol 30-50 part, polyether glycol 30-50 part,
Carbon fiber 2-5 part, hollow glass micropearl 4-8 part,
Linking agent 1-2 part, stablizer 2-3 part;
B component:
Isocyanic ester 20-30 part,
Polyolefin block formula multipolymer OBCs1.5-3 part.
2. a kind of modified carbon fiber/compound polyurethane material as claimed in claim 1, is characterized in that, with parts by weight, comprises following component:
Component A:
Polyester polyol 45 parts, polyether glycol 30 parts,
2.5 parts, carbon fiber, hollow glass micropearl 5 parts,
Linking agent 2 parts, stablizer 2.5 parts;
B component:
Isocyanic ester 30 parts,
Polyolefin block formula multipolymer OBCs2 part.
3. a kind of modified carbon fiber/compound polyurethane material as claimed in claim 1, it is characterized in that, described polyester polyol is one or more mixing in poly-adipate glycol propylene glycol ester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol, polycarbonate polyol.
4. a kind of modified carbon fiber/compound polyurethane material as claimed in claim 1, is characterized in that, described polyether glycol is one or more mixing in Amino Terminated polyether(ATPE) polyvalent alcohol, 6305 polyether glycols, low functionality polyether glycol.
5. a kind of modified carbon fiber/compound polyurethane material as claimed in claim 1, is characterized in that, the diameter of described carbon fiber is 1-2 μm, and length is 5-10 μm.
6. a kind of modified carbon fiber/compound polyurethane material as claimed in claim 1, is characterized in that, the size of described hollow glass micropearl is 20-30nm.
7. a kind of modified carbon fiber/compound polyurethane material as claimed in claim 1, is characterized in that, described isocyanic ester is 4, one or more mixing in 4 '-diphenylmethanediisocyanate, isophorone diisocyanate.
8. a kind of modified carbon fiber/compound polyurethane material as claimed in claim 1, is characterized in that, described linking agent is silane coupling agent.
9. the preparation method of a kind of modified carbon fiber/compound polyurethane material as described in as arbitrary in claim 1 to 8, is characterized in that, comprise the following steps:
(1) by polyester polyol, polyether glycol, carbon fiber, hollow glass micropearl, linking agent and stablizer mixing and stirring, at 80-100 DEG C, ultrasonic 1-2h, obtains component A;
(2) isocyanic ester, polyolefin block formula multipolymer OBCs are mixed, at 100-120 DEG C, ultrasonic 1-2h, obtains B component;
(3) component A and B component are mixed, be injected into die for molding, obtain modified carbon fiber/compound polyurethane material.
10. the preparation method of a kind of modified carbon fiber/compound polyurethane material as claimed in claim 9, is characterized in that, in step (1), described ultrasonic power is 1000W.
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (6)
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| WO2018060746A1 (en) * | 2016-09-30 | 2018-04-05 | Spencer Coatings Limited | Composition |
| CN109401046A (en) * | 2018-09-10 | 2019-03-01 | 东莞市松研智达工业设计有限公司 | A kind of PP composite material and preparation method |
| CN109503793A (en) * | 2018-11-09 | 2019-03-22 | 广东电网有限责任公司 | A kind of carbon fibre composite and the preparation method and application thereof |
| CN109776748A (en) * | 2019-01-22 | 2019-05-21 | 天津爱德加科技有限公司 | A kind of full hydraulic matter polyurethane foam composition polyethers of high temperature resistant, hard polyurethane foams and preparation method thereof |
| CN110450488A (en) * | 2019-07-31 | 2019-11-15 | 山东大学 | A kind of preparation method of different stack layer carbon cloth/TPU composite materials with high electromagnetic shielding performance |
| CN116120825A (en) * | 2023-02-14 | 2023-05-16 | 上海正欧实业有限公司 | High-hardness polyurethane floor coating and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018060746A1 (en) * | 2016-09-30 | 2018-04-05 | Spencer Coatings Limited | Composition |
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| CN109401046A (en) * | 2018-09-10 | 2019-03-01 | 东莞市松研智达工业设计有限公司 | A kind of PP composite material and preparation method |
| CN109503793A (en) * | 2018-11-09 | 2019-03-22 | 广东电网有限责任公司 | A kind of carbon fibre composite and the preparation method and application thereof |
| CN109776748A (en) * | 2019-01-22 | 2019-05-21 | 天津爱德加科技有限公司 | A kind of full hydraulic matter polyurethane foam composition polyethers of high temperature resistant, hard polyurethane foams and preparation method thereof |
| CN110450488A (en) * | 2019-07-31 | 2019-11-15 | 山东大学 | A kind of preparation method of different stack layer carbon cloth/TPU composite materials with high electromagnetic shielding performance |
| CN116120825A (en) * | 2023-02-14 | 2023-05-16 | 上海正欧实业有限公司 | High-hardness polyurethane floor coating and preparation method thereof |
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