CN1302031C - Use of methacrylic acid tetradecyl ester-maleic anhydride copolymer - Google Patents
Use of methacrylic acid tetradecyl ester-maleic anhydride copolymer Download PDFInfo
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- CN1302031C CN1302031C CNB2005100246479A CN200510024647A CN1302031C CN 1302031 C CN1302031 C CN 1302031C CN B2005100246479 A CNB2005100246479 A CN B2005100246479A CN 200510024647 A CN200510024647 A CN 200510024647A CN 1302031 C CN1302031 C CN 1302031C
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- maleic anhydride
- methacrylic acid
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- tetradecyl ester
- random copolymers
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Abstract
The present invention discloses an application of tetradecyl methylacrylate-maleic anhydride copolymers on glass fiber reinforced polypropylene composite materials. The copolymer of the present invention is a macromolecular interface modifying agent and is compounded with polypropylene after a glass fiber surface treated by a coupling agent, the shearing strength of interfaces is improved, and the bending property of composite materials is improved. The copolymer is a flexible interface layer and has the functions of passivation of fractured notches and increase of fracture initiation energy and propagation energy. In addition, the copolymer can prevent fragile fiber surfaces from being abraded in forming, the surface defects of fibers are made up, and better impact strength is generated.
Description
Technical field
The present invention relates to the new purposes of methacrylic acid 14 esters-maleic anhydride copolymer, be specifically related to its application as the macromole interface modifier of glass fiber reinforced polypropylene composite material.
Background technology
Owing to have high specific strength, good advantages such as thermal characteristics, insulating property and water resistance, glass fiber reinforced polypropylene composite material (being called for short PP/GF) is the analog thermoplastic matrix material very rapidly of materialogy field development in recent years.The key of preparation high-performance PP/GF is the interface binding intensity that will improve between polarity glass and the nonpolar PP, and the uncompatibility of polypropylene and glass causes the two compound interface in conjunction with bad.Therefore in order to improve the interface binding intensity of the two, the MALEIC ANHYDRIDE graft polyolefin is introduced in glass and the polypropylene matrix as interface modifier and compatilizer.Two kinds of introducing methods are arranged usually, and a kind of is to add the MALEIC ANHYDRIDE graft polyolefin in matrix, and matrix is carried out blending and modifying, and another kind is to apply the MALEIC ANHYDRIDE graft polyolefin at fiberglass surfacing.
Though the preparation of MALEIC ANHYDRIDE graft polyolefin is by wide coverage, but the percentage of grafting of MALEIC ANHYDRIDE and transformation efficiency are still very low, and also there is the part degraded in polyolefine in graft reaction, therefore, between glass fibre and polyolefin substrate, introduce the MALEIC ANHYDRIDE graft polyolefin with above-mentioned two kinds of methods and improve both affinities, can only partly improve biphase interface bonding, make the tensile strength and the flexural strength acquisition improvement to a certain degree of matrix material, and the polyolefinic introducing of MALEIC ANHYDRIDE do not make the toughness of matrix material increase, and the shock strength of matrix material does not improve.
Summary of the invention
The technical issues that need to address of the present invention are the application that disclose a kind of methacrylic acid 14 esters-MALEIC ANHYDRIDE random copolymers, to overcome the defective that prior art exists, satisfy the needs in relevant field.
Said methacrylic acid 14 esters of the present invention-MALEIC ANHYDRIDE random copolymers has had disclosed report in the patent of the application number 03141992 of contriver Dong Qing, and its structure fragment is as follows:
Wherein: m=155～200, n=210～230
Its molecular weight is 6 * 10
4～7 * 10
4
The preparation method of methacrylic acid 14 esters of the present invention-MALEIC ANHYDRIDE random copolymers comprises the steps:
In inert gas atmosphere, with MALEIC ANHYDRIDE in solvent, in the presence of initiator, react with methacrylic acid 14 esters, reaction times is 4～8 hours, temperature of reaction is 50～70 ℃, collects methacrylic acid 14 esters-MALEIC ANHYDRIDE random copolymers then from reaction product.
Said solvent is selected from a kind of or its mixture in toluene, dimethylbenzene or the tetrahydrofuran (THF);
Said initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), BPO dibenzoyl peroxide, and the trade mark of producing as Shanghai reagent one factory is the Diisopropyl azodicarboxylate initiator of AIBN;
The mol ratio of MALEIC ANHYDRIDE and methacrylic acid 14 esters is:
MALEIC ANHYDRIDE: methacrylic acid 14 esters=6: 4～8: 2;
In the solvent, the concentration of MALEIC ANHYDRIDE is 0.1～0.4 gram/ml;
The initiator mole dosage is 1/1000～2/1000 of a total moles monomer.
Said rare gas element preferred nitrogen.
Methacrylic acid 14 esters of the present invention-MALEIC ANHYDRIDE random copolymers can be used for preparing glass fiber reinforced polypropylene composite material, concrete application method comprises the steps: 1～10min is flooded in glass felt elder generation in the aqueous solution of the silane coupling A 1100 of 0.1～1.0% (mass ratio), take out dry, being impregnated in methacrylic acid 14 esters-MALEIC ANHYDRIDE random copolymers weight concentration then is 0.1～1.0% xylene solution, take out, react 0.5～2h down at 105～120 ℃;
To restrain polypropylene matrix then, to be pressed into thickness be thin slice about 0.5～2mm, then with polypropylene and glass felt crossing stack lay between upper and lower template, compression molding obtains the PP/GF sheet material.
The temperature of composite material moulded moulding is: 170 ℃～200 ℃;
The pressure of compression molding is: 5～10Mpa;
The time of compression molding is: 2～6min.
Measure anhydride content in the multipolymer with the KOH/ ethanol solution.
Methacrylic acid 14 esters-MALEIC ANHYDRIDE random copolymers is as a kind of novel macromole interface modifier, be coated in behind the glass surface of coupling agent treatment compound with polypropylene, the long side chain and the polypropylene matrix consistency of multipolymer are good, molecular chain diffuses to form firm mutual entanglement mutually, and the maleic acid anhydride group of multipolymer and the coupling agent strong interactions such as forming the chemical bond combination that can react, therefore, can improve the interface bond strength of compound system, improve the bending property of compound system.
Than the MALEIC ANHYDRIDE graft polyolefin, this novel interface modifier has higher anhydride content on the one hand, can obtain better interface binding intensity with consumption still less.On the other hand, better interface binding intensity can cause the raising of interface shear strength usually, and reduces shock strength.Therefore in order to compensate the reduction of shock strength, the interface flexible layer is introduced into.
Embodiment
Experimental raw:
Polypropylene Y2600 (Shanghai petrochemical industry plastic section), glass is provided by tai shan glass company limited, coupling agent γ-An Bingjisanyiyangjiguiwan A1100, initiator Diisopropyl azodicarboxylate and monomer methacrylic acid 14 esters are commercially available, and MALEIC ANHYDRIDE and solvent all are untreated and directly use.The MALEIC ANHYDRIDE graft polypropylene is commercially available.
Embodiment 1
Polyreaction is carried out in the four-hole round-bottomed flask, and flask inserts ventpipe, thermometer, agitator, heating in water bath, 60 ℃ of constant temperature.Insert the 300mL solvent toluene, drop into 60 gram MALEIC ANHYDRIDE, stirring is opened in logical nitrogen protection after about 30 minutes.After MALEIC ANHYDRIDE is dissolved fully, add 75 gram methacrylic acids, 14 esters, treat that monomer mixes the back and adds 0.15 gram initiator A IBN toluene solution initiation reaction, in nitrogen atmosphere, continue to stir 6h.Reaction product is filtered with methanol extraction, and the gained polymerisate dissolves with tetrahydrofuran (THF) again, and methyl alcohol precipitates once more, to remove impurity.Polymerisate to constant weight, promptly obtains target product of the present invention with vacuum-drying.
Anhydride content is 48.2%.
Embodiment 2
Adopt the method identical with embodiment 1, wherein: drop into MALEIC ANHYDRIDE 75 grams, add methacrylic acid 14 esters 94 and restrain, temperature of reaction is 50 ℃, and the reaction times is 8 hours.
Anhydride content is 44.2%.
Embodiment 3
Adopt the method identical, wherein: drop into MALEIC ANHYDRIDE 90 grams, lead to nitrogen protection and open stirring after about 30 minutes with embodiment 1.After MALEIC ANHYDRIDE is dissolved fully, add methacrylic acid 14 esters 65 grams, anhydride content is 42.1%.Temperature of reaction is 70 ℃, and the reaction times is 4 hours.
Embodiment 4
With 120 * 120 * 4mm
3The glass felt floods 5min in the aqueous solution of 150ml 0.6% (mass ratio) silane coupling A 1100, dry 1h makes reacting completely of glass and coupling agent under 70 ℃ in vacuum drying oven, be impregnated in MALEIC ANHYDRIDE then: the multipolymer weight concentration of methacrylic acid 14 esters=7: 3 (mol ratio) is 0.3% xylene solution 200ml, put into baking oven, 110 ℃ are reacted 1h down.
With 8.8 gram polypropylene matrixs is thin slice about 1mm with the frame mould being pressed into thickness on the vulcanizing press earlier, then with five strata propylene and four layers of glass felt lamination lay between upper and lower template, on vulcanizing press, system is preheated to 180 ℃, compound 5min under the pressure of 6MPa then, take out cooling fast, die sinking promptly obtains the PP/GF sheet material.
Embodiment 5
Adopt the method identical with embodiment 4.With 120 * 120 * 4mm
3The glass felt floods 5min in the aqueous solution of 150ml 0.6% (mass ratio) silane coupling A 1100, dry 1h makes reacting completely of glass and coupling agent under 70 ℃ in vacuum drying oven, be impregnated in MALEIC ANHYDRIDE then: the multipolymer weight concentration of methacrylic acid 14 esters=6: 4 (mol ratio) is 0.3% toluene solution 200ml, put into baking oven, 110 ℃ are reacted 1h down.
With 8.8 gram polypropylene matrixs is thin slice about 1mm with the frame mould being pressed into thickness on the vulcanizing press earlier, then with five strata propylene and four layers of glass felt lamination lay between upper and lower template, on vulcanizing press, system is preheated to 190 ℃, compound 5min under the pressure of 9MPa then, take out cooling fast, die sinking promptly obtains the PP/GF sheet material.
Embodiment 6
Adopt the method identical with embodiment 4.With 120 * 120 * 4mm
3The glass felt floods 5min in the aqueous solution of 150ml 0.6% (mass ratio) silane coupling A 1100, dry 1h makes reacting completely of glass and coupling agent under 70 ℃ in vacuum drying oven, be impregnated in MALEIC ANHYDRIDE then: the multipolymer weight concentration of methacrylic acid 14 esters=8: 2 (mol ratio) is 0.3% tetrahydrofuran solution 200ml, put into baking oven, 100 ℃ are reacted 1h down.
With 8.8 gram polypropylene matrixs is thin slice about 1mm with the frame mould being pressed into thickness on the vulcanizing press earlier, then with five strata propylene and four layers of glass felt lamination lay between upper and lower template, on vulcanizing press, system is preheated to 170 ℃, compound 4min under the pressure of 5MPa then, take out cooling fast, die sinking promptly obtains the PP/GF sheet material.
Embodiment 7
Adopt the method identical with embodiment 4.With 120 * 120 * 4mm
3The glass felt floods 5min in the aqueous solution of 150ml 0.6% (mass ratio) silane coupling A 1100, dry 1h makes reacting completely of glass and coupling agent under 70 ℃ in vacuum drying oven, be impregnated in MALEIC ANHYDRIDE then: the multipolymer weight concentration of methacrylic acid 14 esters=7: 3 (mol ratio) is 0.4% tetrahydrofuran solution 200ml, put into baking oven, 110 ℃ are reacted 1h down.
With 8.8 gram polypropylene matrixs is thin slice about 1mm with the frame mould being pressed into thickness on the vulcanizing press earlier, then with five strata propylene and four layers of glass felt lamination lay between upper and lower template, on vulcanizing press, system is preheated to 190 ℃, compound 6min under the pressure of 10MPa then, take out cooling fast, die sinking promptly obtains the PP/GF sheet material.
Embodiment 8
Adopt the method identical with embodiment 4.With 120 * 120 * 4mm
3The glass felt floods 5min in the aqueous solution of 150ml 0.6% (mass ratio) silane coupling A 1100, dry 1h makes reacting completely of glass and coupling agent under 70 ℃ in vacuum drying oven, be impregnated in MALEIC ANHYDRIDE then: the multipolymer weight concentration of methacrylic acid 14 esters=7: 3 (mol ratio) is 0.6% xylene solution 200ml, put into baking oven, 110 ℃ are reacted 1h down.
With 8.8 gram polypropylene matrixs is thin slice about 1mm with the frame mould being pressed into thickness on the vulcanizing press earlier, then with five strata propylene and four layers of glass felt lamination lay between upper and lower template, on vulcanizing press, system is preheated to 170 ℃, compound 5min under the pressure of 8MPa then, take out cooling fast, die sinking promptly obtains the PP/GF sheet material.
Embodiment 9
Adopt the method identical with embodiment 4.With 120 * 120 * 4mm
3The glass felt floods 5min in the aqueous solution of 150ml 0.6% (mass ratio) silane coupling A 1100, dry 1h makes reacting completely of glass and coupling agent under 70 ℃ in vacuum drying oven, be impregnated in MALEIC ANHYDRIDE then: the multipolymer weight concentration of methacrylic acid 14 esters=7: 3 (mol ratio) is 0.1% toluene solution 200ml, put into baking oven, 110 ℃ are reacted 1h down.
With 8.8 gram polypropylene matrixs is thin slice about 1mm with the frame mould being pressed into thickness on the vulcanizing press earlier, then with five strata propylene and four layers of glass felt lamination lay between upper and lower template, on vulcanizing press, system is preheated to 200 ℃, compound 4min under the pressure of 5MPa then, take out cooling fast, die sinking promptly obtains the PP/GF sheet material.
Embodiment 10
Adopt the method identical with embodiment 4.With 120 * 120 * 4mm
3The glass felt floods 5min in the aqueous solution of 150ml 0.6% (mass ratio) silane coupling A 1100, dry 1h makes reacting completely of glass and coupling agent under 70 ℃ in vacuum drying oven, the weight concentration that is impregnated in the MALEIC ANHYDRIDE graft polypropylene then is 0.3% toluene solution 200ml, put into baking oven, 110 ℃ are reacted 1h down.
With 8.8 gram polypropylene matrixs is thin slice about 1mm with the frame mould being pressed into thickness on the vulcanizing press earlier, then with five strata propylene and four layers of glass felt lamination lay between upper and lower template, on vulcanizing press, system is preheated to 180 ℃, compound 5min under the pressure of 6MPa then, take out cooling fast, die sinking promptly obtains the PP/GF sheet material.
The sheet material that obtains is milled into standard test specimen with milling machine, on Ray-Ran impact experiment machine, record material notched izod shock strength, 25 ℃ of temperature, mechanical v-notch is gone up mensuration material bending performance at Zwick z010 (Germany).
The mechanical property of matrix material (fibre content is 33%) sees Table 1.Experimental result shows that the flexural strength of matrix material, modulus in flexure and shock strength all are higher than the mechanical property of untreated PP/GF.
When the glass felt that has applied A1100 is handled with copolymer solution, glass felt and copolymer coated big generation chemical reaction are as follows: at first the A1100 hydrolysis generates Si-OH, the part Si on Si-OH and glass surface-OH condensation forms firm chemical bond and combines between fiber and coupling agent.Simultaneously, the amino of A1100 end and the MAH of multipolymer react, and cause the chemical bonding of glass and interfacial layer.In addition, the long side chain of multipolymer can close the PP matrix and form very strong physical entanglement, has improved the consistency of PP matrix and interfacial layer, and the flexural strength of PP/GF is improved.Experimental result shows that flexural strength and modulus all increase along with the increase of MAH monomer ratio.
PP/GF can and break by the distortion of fibre breakage, matrix, interface peel and fiber are extracted etc. absorbs impact energy.After the glass felt was handled with copolymer solution, because the toughness of multipolymer has been introduced the compliant interface layer, the compliant interface layer with elastomeric characteristic can carry out bigger deformation, and the specific rigidity matrix can absorb more fracture propagation energy.The compliant interface layer can passivation the fracture breach, increase fracture energy of initiation and propagation energy.In addition, it can protect the fragile fibre surface to avoid wearing and tearing in moulding process, remedies the fiber surface defective, causes better shock strength.
The multipolymer of table 1 different monomers proportioning is to the influence of PP/GF mechanical property
| Monomer ratio | Shock strength (KJ/m 2) | Flexural strength (MPa) | Modulus in flexure (MPa) |
| The copolymer of copolymer embodiment 3 of copolymer embodiment 2 of embodiment 1 is untreated | 19.7 29.1 40.5 42.5 | 39.1 57.0 54.7 42.1 | 2569.8 3001.7 2802.8 2594.9 |
Experimental result shows, compares with untreated PP/GF, and the PP/GF mechanical property of handling with multipolymer of the present invention all is significantly increased.
Compare with the PP-g-MAH interfacial layer, interfacial layer of the present invention has good flexible, and this helps bigger matrix distortion, and the energy of extracting absorption by fiber is higher.Therefore, need not to introduce elastomerics at the interface, PP/GF is added tough.Experimental result sees Table 2.
The coating of table 2 different concns is to the influence of PP/GF mechanical property
| The properties-correcting agent of different concns | Shock strength (KJ/m 2) | Flexural strength (MPa) | Modulus in flexure (MPa) |
| 0.6% copolymer, 0.4% copolymer, 0.3% copolymer, 0.1% copolymer 0.6%PP-g-MAH 0.4%PP-g-MAH 0.3%PP-g-MAH 0.1%PP-g-MAH is untreated | 19.7 26.5 30.1 40.3 25.2 26.8 22.4 20.7 20.1 | 39.1 53.1 54.1 54.6 44.1 41.7 40.5 39.8 39.3 | 2569.8 2777.0 2790.8 2802.8 2760.4 2680.4 2620.8 2583.8 2572.8 |
Claims (4)
1. the application of methacrylic acid tetradecyl ester-maleic anhydride random copolymers is characterized in that, is used to prepare glass fiber reinforced polypropylene composite material, and the structure fragment of described methacrylic acid tetradecyl ester-maleic anhydride random copolymers is as follows:
Wherein: m=155～200, n=210～230.
2. application according to claim 1 is characterized in that, methacrylic acid tetradecyl ester-maleic anhydride random copolymers molecular weight is 6 * 10
4～7 * 10
4
3. application according to claim 1, it is characterized in that, 1～10min is flooded in elder generation in the aqueous solution of the silane coupling A 1100 of 0.1～1.0% mass ratio with the glass felt, take out dry, be impregnated in methacrylic acid tetradecyl ester-maleic anhydride random copolymers weight concentration then and be 0.1～1.0% xylene solution, take out, react 0.5～2h down at 105～120 ℃;
Then this polypropylene matrix is pressed into thickness and is the thin slice about 0.5～2mm, then with polypropylene and glass felt crossing stack lay between upper and lower template, compression molding obtains the glass-reinforced polypropylene composite sheet.
4. the application of methacrylic acid tetradecyl ester-maleic anhydride random copolymers according to claim 3 is characterized in that:
The temperature of composite material moulded moulding is: 170 ℃～200 ℃;
The pressure of compression molding is: 5～10Mpa;
The time of compression molding is: 2～6min.
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| CNB2005100246479A CN1302031C (en) | 2005-03-25 | 2005-03-25 | Use of methacrylic acid tetradecyl ester-maleic anhydride copolymer |
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| CN1302031C true CN1302031C (en) | 2007-02-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10465027B2 (en) | 2014-12-18 | 2019-11-05 | Evonik Oil Additives Gmbh | Method for the preparation of copolymers of alkyl methacrylates and maleic anhydride |
| US10703840B2 (en) | 2014-12-18 | 2020-07-07 | Evonik Operations Gmbh | Method for the preparation of copolymers of alkyl methacrylates and maleic anhydride |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402571C (en) * | 2006-02-07 | 2008-07-16 | 中国石油化工股份有限公司 | Amphiphilic block copolymer and its preparing method and use in preparing composite material |
| CN105029949B (en) * | 2015-08-18 | 2019-02-01 | 振石控股集团有限公司 | A kind of beddo flexible bed board and its forming method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6044535A (en) * | 1983-08-23 | 1985-03-09 | Asahi Fiber Glass Co Ltd | Reinforced thermoplastic resin |
| CN1486997A (en) * | 2003-07-24 | 2004-04-07 | 华东理工大学 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
| CN1487128A (en) * | 2003-07-31 | 2004-04-07 | 华东理工大学 | Antistatic polypropylene fiber and its prepn process |
-
2005
- 2005-03-25 CN CNB2005100246479A patent/CN1302031C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6044535A (en) * | 1983-08-23 | 1985-03-09 | Asahi Fiber Glass Co Ltd | Reinforced thermoplastic resin |
| CN1486997A (en) * | 2003-07-24 | 2004-04-07 | 华东理工大学 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
| CN1487128A (en) * | 2003-07-31 | 2004-04-07 | 华东理工大学 | Antistatic polypropylene fiber and its prepn process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10465027B2 (en) | 2014-12-18 | 2019-11-05 | Evonik Oil Additives Gmbh | Method for the preparation of copolymers of alkyl methacrylates and maleic anhydride |
| US10472444B2 (en) | 2014-12-18 | 2019-11-12 | Evonik Oil Additives Gmbh | Method for the preparation of copolymers of alkyl methacrylates and maleic anhydride |
| US10703840B2 (en) | 2014-12-18 | 2020-07-07 | Evonik Operations Gmbh | Method for the preparation of copolymers of alkyl methacrylates and maleic anhydride |
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| CN1667005A (en) | 2005-09-14 |
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