CN102690397A - Compatilizer for cellulose material reinforced composite material and preparation method for compatilizer - Google Patents
Compatilizer for cellulose material reinforced composite material and preparation method for compatilizer Download PDFInfo
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- CN102690397A CN102690397A CN2012101864755A CN201210186475A CN102690397A CN 102690397 A CN102690397 A CN 102690397A CN 2012101864755 A CN2012101864755 A CN 2012101864755A CN 201210186475 A CN201210186475 A CN 201210186475A CN 102690397 A CN102690397 A CN 102690397A
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Abstract
The invention relates to a compatilizer for a cellulose material reinforced composite material and a preparation method for the compatilizer, and belongs to the technical field of high polymer material modification. A reaction interface compatilizer is prepared by cografting acrylate monomers, styrene, an initiator, polyolefin, a bonding agent and the like on the polyolefin through a solid-phase grafting method. The compatilizer has the advantages that the grafting ratio of functional monomers on a polymer substrate main chain is high, the functional monomers can form covalent bonds with hydroxyl on the surface of a cellulose material efficiently, and the dispersibility of the cellulose material in a plastic substrate is promoted; meanwhile, the macromolecular main chain has proper molecular weight, can be subjected to chain entanglement with the plastic substrate in the composite material to improve the compatibility, has high melting fluidity, can effectively infiltrate the composite material during processing, is closely meshed at the interface to form an interface layer for effectively transmitting stress and effectively relieves fine cracks generated due to deformation of the material, the mechanical properties and water resistance of the composite material are improved, and the application range of the composite material in various fields is widened.
Description
Technical field
The present invention relates to reactive interfacial compatibilizer that a kind of cellulose material reinforced composite materials uses and preparation method thereof, belong to the polymer modification technical field.
Background technology
Continuous development along with polymer science; The quality of macromolecular material is various day by day; With two or more macromolecular material blend compound or add various fillers and plastic substrate compound; Advantage with comprehensive each component property can obtain the more good matrix material of over-all properties, and this type of work is just receiving the extensive concern of each side.But, because the difference of different plastic substrates and carrier performance,, caused in the matrix material each group partition inter-capacitive not good enough like the difference of polarity, surface energy etc., had a strong impact on performance of composites, limited its application.The cellulose material reinforced composite materials, be a kind of be the matrix material that base mateiral and plastics (also can be multiple plastics) are processed mainly by timber or Mierocrystalline cellulose, wherein the glucosides structure of cellulose material is rich in hydroxyl, polarity is higher; And polyolefin substrate is the main body with the carbon carbochain basically, and polarity is lower, and both consistencies are very poor, receives external force and makes time spent stress and be difficult to effectively be delivered on the cellulose material as reinforcing filler, and mechanical property is relatively poor.The interfacial compatibilizer of consistency is just very important between plain type material of therefore, exploitation ability fortifying fibre and plastic substrate.
The cellulose material reinforced composite materials is used interfacial compatibilizer, generally is the function monomer that has two keys and polar group or reactive group is caused through initiator, is grafted on the macromolecular main chain through free radical reaction.Function monomer in the grafting had both improved the polarity of macromolecular main chain, and its reactive group that has can form covalent linkage with the cellulose material surface hydroxyl again simultaneously; And macromolecular main chain since with matrix material in the plastic substrate structural similitude, molecular entanglement can take place with it, thereby has strengthened the consistency of cellulose material and plastic substrate.Present the most widely used function monomer is maleic anhydride (MAH, a MALEIC ANHYDRIDE), and compatible system too single is the major issue of restriction cellulose material reinforced composite materials performance boost.Therefore, the interfacial compatibilizer of other function monomers and novel monomeric preparation is used in exploitation, and crucial meaning is arranged.Simultaneously, traditional interfacial compatibilizer preparation method is solution grafting and fusion-grafting method.Solution method is dissolved in function monomer, initiator, plastic substrate in the solvent jointly reacts, and has the high advantage of percentage of grafting, but needs to use and reclaim high amounts of solvents, and cost is higher; Scorification makes function monomer and plastic substrate generation graft reaction through screw extrusion press in extrusion; Can carry out operate continuously in enormous quantities; But because the extrusion service temperature is high; Side reaction such as polymer chain degraded be prone to taking place cause the macromolecular main chain molecular weight and molecular weight, makes plastic substrate entanglement degradation in itself and the matrix material.These two kinds of traditional methods all have bigger defective, therefore, study the reactive interfacial compatibilizer that a kind of new cellulose material reinforced composite materials is used, and preparation method thereof, just seem very necessary.
Summary of the invention
One of the object of the invention: be to provide the non-maleic anhydride of a kind of use as function monomer, the cellulose material reinforced composite materials of preparation is used interfacial compatibilizer.This interfacial compatibilizer has advantages such as percentage of grafting height, macromolecular main chain molecular weight be suitable, can effectively improve the consistency of cellulose material and plastic substrate, can tangle with plastic substrate generation molecular weight in the matrix material; Improve consistency, have good melt fluidity again, work in-process can effectively soak into matrix material; In tight engagement at the interface; Form the interfacial layer that effectively transmits stress, in addition, the hair line that produces in the time of can also effectively alleviating material deformation; Thereby improve the mechanical property and the water tolerance of cellulose material reinforced composite materials, widened them and used in each field.
Two of the object of the invention: be to provide the preparation method of this cellulose material reinforced composite materials with interfacial compatibilizer.The interfacial compatibilizer that this method makes has function monomer percentage of grafting height, and temperature of reaction is lower, helps graft reaction generation rather than degraded side reaction, and the polyolefin backbone palliating degradation degree is low, advantages such as reaction conditions gentleness.
A kind of cellulose material reinforced composite materials of the present invention is with the preparation method of reactive interfacial compatibilizer; Be to form through the reaction of solid phase grafting method by acrylic ester monomer, vinylbenzene, initiator, polyolefine, interfacial agents etc.; The polyolefin backbone molecular weight is 1000 ~ 6000, and percentage of grafting is 5% ~ 15%.
The weight part consumption of each component is following:
100 parts of polyolefine
10 ~ 30 parts of acrylic ester monomers
10 ~ 30 parts of vinylbenzene
0.5 ~ 3 part of initiator
10 ~ 20 parts of interfacial agents
Described acrylic ester monomer is: one or more in vinylformic acid, methylacrylic acid, the SY-Monomer G.
Described initiator is: one or more in Lucidol, Diisopropyl azodicarboxylate, Di Cumyl Peroxide 99, the peroxidized t-butyl perbenzoate.
Described polyolefine is: one or more in LLDPE, new LDPE (film grade), high density polyethylene(HDPE), the Vestolen PP 7052.
Described interfacial agents is: toluene, YLENE, 1,2, one or more in the 4-trichlorobenzene.
The concrete preparation method of reactive interfacial compatibilizer of the present invention is: polyolefine is added in the four-hole boiling flask, and slowly the mixture of dropwise addition of acrylic acid esters monomer, vinylbenzene, initiator, interfacial agents composition feeds nitrogen, stirring at normal temperature 0.5 ~ 2 hour simultaneously.Under 100 ~ 140 ℃, reacted 0.5 ~ 2 hour subsequently.
When being applied to extrusion by melting and preparing plain type of material prepn matrix material of polypropylene matrix and dimension; But by the inventive method synthetic reactive interfacial compatibilizer; Its addition is not less than 5% (weight ratio); Adding cellulose material is: cellulose materials such as wood powder, sawdust, wood shavings, flax fiber, old and useless newspaper, cotton spinning mill tankage, stalk, rice husk, corn cob; The miscellany of one or more after process pulverizing, sieve (like 60 orders), drying etc. are handled, weight accounts for more than 40%, thereby can make the mechanical property of such matrix material and water tolerance obtain preferable raising.
Compare with existing compatilizer, outstanding and the remarkable advantage of compatilizer of the present invention are:
1. the compatilizer percentage of grafting through the preparation of solid phase grafting method is high, and the reflecting point that can form covalent linkage with the hydroxyl on cellulose material surface is many, can combine closely with cellulose material; This preparation method is because temperature of reaction is lower than fusion-grafting method; The polyolefin backbone palliating degradation degree is low; Have the appropriate molecular amount, can tangle with plastic substrate generation molecular weight in the matrix material and improve consistency, have good melt fluidity again; Work in-process can effectively soak into matrix material; Form the interfacial layer of effective transmission stress in tight engagement at the interface, the hair line that produces in the time of can also effectively alleviating material deformation in addition, thus improve cellulose material reinforced composite materials mechanical property and water tolerance.
2. compatilizer of the present invention; Can significantly improve the dispersiveness of cellulose material in the matrix material, prevent the reunion of cellulose material in matrix material, cellulose material reinforced composite materials interface is improved; Effect is excellent, and its mechanical property can improve.
3. the method for preparing compatilizer among the present invention is easy and simple to handle, and technology is terse, and the high percentage of grafting of ability simple realization interfacial compatibilizer function monomer need not use high amounts of solvents; Temperature of reaction is lower than scorification, can effectively reduce polyolefin backbone degraded side reaction again.
4. compatilizer of the present invention can effectively improve cellulose material reinforced composite materials mechanical property and water tolerance.
Embodiment
Embodiment 1:
The 20g Vestolen PP 7052 is added in the four-hole boiling flask, slowly drip the mixture of 2g SY-Monomer G, 2g vinylbenzene, 0.2g Lucidol, 2g YLENE, feed nitrogen simultaneously, stirring at normal temperature 1 hour.Under 120 ℃, reacted 1 hour subsequently.The reaction back that finishes is an extractant with acetone, and extracting 24 hours continuously in Soxhlet's apparatus after removing unreacted or the function monomer of homopolymerization taking place, is put into baking oven 100 ℃ of following successive dryings 24 hours, obtains the purified interfacial compatibilizer, and its percentage of grafting is 8.509%
Be applied to extrusion by melting and prepare the polypropylene-base matrix material; Add 5% (weight % ratio) at interfacial compatibilizer; Wood powder (60 orders; Water cut is lower than 1%) added 40% o'clock, obtained matrix material is compared with the matrix material that commercially available maleic anhydride type interfacial compatibilizer prepares under the same process condition, and tensile strength is brought up to 34.3MPa by 30.5MPa; Notched Izod impact strength is by 6.1kJ/m
2Bring up to 6.4 kJ/m
2Water-intake rate is reduced to 6.9% by 8.6%.
Embodiment 2:
The 20g Vestolen PP 7052 is added in the four-hole boiling flask, slowly drip the mixture of 3g SY-Monomer G, 3g vinylbenzene, 0.2g Lucidol, 2g YLENE, feed nitrogen simultaneously, stirring at normal temperature 1 hour.Under 120 ℃, reacted 1 hour subsequently.The reaction back that finishes is an extractant with acetone, and extracting 24 hours continuously in Soxhlet's apparatus after removing unreacted or the function monomer of homopolymerization taking place, is put into baking oven 100 ℃ of following successive dryings 24 hours, obtains the purified interfacial compatibilizer, and its percentage of grafting is 9.402%.
Be applied to extrusion by melting and prepare the polypropylene-base matrix material; Add 5% (weight ratio) at interfacial compatibilizer; Sawdust (60 orders; Water cut is lower than 1%) added 40% o'clock, obtained matrix material is compared with the matrix material that commercially available maleic anhydride type interfacial compatibilizer prepares under the same process condition, and tensile strength is brought up to 35.7MPa by 30.2MPa; Notched Izod impact strength is by 5.9kJ/m
2Bring up to 6.3 kJ/m
2Water-intake rate is reduced to 6.3% by 8.1%.
Embodiment 3:
The 20g new LDPE (film grade) is added in the four-hole boiling flask, slowly drip the mixture of 4g SY-Monomer G, 3g vinylbenzene, 0.3g Lucidol, 2g YLENE, feed nitrogen simultaneously, stirring at normal temperature 1 hour.Under 120 ℃, reacted 1 hour subsequently.The reaction back that finishes is an extractant with acetone, and extracting 24 hours continuously in Soxhlet's apparatus after removing unreacted or the function monomer of homopolymerization taking place, is put into baking oven 100 ℃ of following successive dryings 24 hours, obtains the purified interfacial compatibilizer, and its percentage of grafting is 7.791%.
Be applied to extrusion by melting and prepare polyethylene based composition; Add 5% (weight ratio) at interfacial compatibilizer; Wood shavings (60 orders; Water cut is lower than 1%) added 50% o'clock, obtained matrix material is compared with the matrix material that commercially available maleic anhydride type interfacial compatibilizer prepares under the same process condition, and tensile strength is brought up to 32.1MPa by 29.4MPa; Notched Izod impact strength is by 5.5kJ/m
2Bring up to 5.9 kJ/m
2Water-intake rate is reduced to 8.7% by 11.2%.
Embodiment 4:
The 20g high density polyethylene(HDPE) is added in the four-hole boiling flask, slowly drip the mixture of 3g SY-Monomer G, 3g vinylbenzene, 0.6g Lucidol, 2g YLENE, feed nitrogen simultaneously, stirring at normal temperature 1 hour.Under 120 ℃, reacted 1 hour subsequently.Reacting the back that finishes is extractant with acetone; Continuously extracting 24 hours in Soxhlet's apparatus after removing unreacted or the function monomer of homopolymerization taking place, is put into baking oven 100 ℃ of following successive dryings 24 hours; Obtain the purified interfacial compatibilizer, its percentage of grafting is 11.256%.
Be applied to extrusion by melting and prepare the polypropylene-base matrix material; Add 5% (weight ratio) at interfacial compatibilizer; Wood powder (60 orders; Water cut is lower than 1%) added 40% o'clock, obtained matrix material is compared with the matrix material that commercially available maleic anhydride type interfacial compatibilizer prepares under the same process condition, and tensile strength is brought up to 36.9MPa by 31.1MPa; Notched Izod impact strength is by 6.0kJ/m
2Bring up to 6.5 kJ/m
2Water-intake rate is reduced to 5.2% by 7.8%.
Embodiment 5:
The 20g Vestolen PP 7052 is added in the four-hole boiling flask, slowly drip the mixture of 3g SY-Monomer G, 3g vinylbenzene, 0.3g Lucidol, 2g YLENE, feed nitrogen simultaneously, stirring at normal temperature 1 hour.Under 100 ℃, reacted 2 hours subsequently.The reaction back that finishes is an extractant with acetone, and extracting 24 hours continuously in Soxhlet's apparatus after removing unreacted or the function monomer of homopolymerization taking place, is put into baking oven 100 ℃ of following successive dryings 24 hours, obtains the purified interfacial compatibilizer, and percentage of grafting is 8.210%.
Be applied to extrusion by melting and prepare the polypropylene-base matrix material; Add 5% (weight ratio) at interfacial compatibilizer; Stalk (60 orders; Water cut is lower than 1%) added 40% o'clock, obtained matrix material is compared with the matrix material that commercially available maleic anhydride type interfacial compatibilizer prepares under the same process condition, and tensile strength is brought up to 35.0MPa by 30.9MPa; Notched Izod impact strength is by 5.9kJ/m
2Bring up to 6.5 kJ/m
2Water-intake rate is reduced to 7.9% by 9.6%.
Embodiment 6:
The 40g Vestolen PP 7052 is added in the four-hole boiling flask, slowly drip the mixture of 6g SY-Monomer G, 6g vinylbenzene, 0.8g Lucidol, 4g YLENE, feed nitrogen simultaneously, stirring at normal temperature 1 hour.Under 130 ℃, reacted 1 hour subsequently.The reaction back that finishes is an extractant with acetone, and extracting 24 hours continuously in Soxhlet's apparatus after removing unreacted or the function monomer of homopolymerization taking place, is put into baking oven 100 ℃ of following successive dryings 24 hours, obtains the purified interfacial compatibilizer, and its percentage of grafting is 6.305%.
Be applied to extrusion by melting and prepare the polypropylene-base matrix material; Add 5% (weight ratio) at interfacial compatibilizer; Wood powder (60 orders; Water cut is lower than 1%) added 40% o'clock, obtained matrix material is compared with the matrix material that commercially available maleic anhydride type interfacial compatibilizer prepares under the same process condition, and tensile strength is brought up to 32.3MPa by 29.1MPa; Notched Izod impact strength is by 6.1kJ/m
2Bring up to 6.4 kJ/m
2Water-intake rate is reduced to 7.6% by 9.1%.
Embodiment 7:
The 30g LLDPE is added in the four-hole boiling flask, and slowly the mixture of Dropwise 5 g SY-Monomer G, 5g vinylbenzene, 0.5g Lucidol, 4g YLENE feeds nitrogen, stirring at normal temperature 1 hour simultaneously.Under 110 ℃, reacted 2 hours subsequently.The reaction back that finishes is an extractant with acetone, and extracting 24 hours continuously in Soxhlet's apparatus after removing unreacted or the function monomer of homopolymerization taking place, is put into baking oven 100 ℃ of following successive dryings 24 hours, obtains the purified interfacial compatibilizer, and its percentage of grafting is 7.098%.
Be applied to extrusion by melting and prepare the polypropylene-base matrix material; Add 5% (weight ratio) at interfacial compatibilizer; Cotton spinning mill tankage (water cut is lower than 1%) added 40% o'clock; Obtained matrix material is compared with the matrix material that commercially available maleic anhydride type interfacial compatibilizer prepares under the same process condition, and tensile strength is brought up to 30.1MPa by 27.9MPa; Notched Izod impact strength is by 4.7kJ/m
2Bring up to 5.2 kJ/m
2Water-intake rate is reduced to 7.1% by 8.3%.
Claims (7)
1. one kind is main chain with the polyolefine; Acrylic ester monomer is a function monomer, and vinylbenzene is the cografting monomer, adds initiator and interfacial agents; Through the solid phase grafting method; Obtain the preparation method of the reactive interfacial compatibilizer that the cellulose material reinforced composite materials uses, it is characterized in that the reactive interfacial compatibilizer that this matrix material is used, its preparation process is following:
Polyolefine is added in the four-hole boiling flask, and slowly the mixture of dropwise addition of acrylic acid esters monomer, vinylbenzene, initiator and interfacial agents composition feeds nitrogen, stirring at normal temperature 0.5 ~ 2 hour simultaneously; Under 100 ~ 140 ℃, reacted 0.5 ~ 2 hour subsequently, the polyolefin backbone molecular weight is 1000 ~ 6000 in this interfacial compatibilizer, and percentage of grafting is 5% ~ 15%; The weight part consumption of each component is following:
100 parts of polyolefine
10 ~ 30 parts of acrylic ester monomers
10 ~ 30 parts of vinylbenzene
0.5 ~ 3 part of initiator
10 ~ 20 parts of interfacial agents.
2. reactive interfacial compatibilizer preparation method according to claim 1 is characterized in that described polyolefine is: one or more in LLDPE, new LDPE (film grade), high density polyethylene(HDPE), the Vestolen PP 7052.
3. reactive interfacial compatibilizer preparation method according to claim 1 is characterized in that described acrylic ester monomer is: one or more in vinylformic acid, methylacrylic acid, the SY-Monomer G.
4. reactive interfacial compatibilizer preparation method according to claim 1 is characterized in that described initiator is: one or more in Lucidol, Diisopropyl azodicarboxylate, Di Cumyl Peroxide 99, the peroxidized t-butyl perbenzoate.
5. reactive interfacial compatibilizer preparation method according to claim 1 is characterized in that described interfacial agents is: toluene, YLENE, 1,2, one or more in the 4-trichlorobenzene.
6. reactive interfacial compatibilizer preparation method according to claim 1; When it is characterized in that plain type of material prepn matrix material of described polypropylene matrix and dimension; Reactive interfacial compatibilizer, its addition are not less than 5% (weight ratio), add cellulose material weight and account for more than 40%.
7. according to claim 1 or 6 described reactive interfacial compatibilizer preparing methods; It is characterized in that the plain type material of described dimension is: cellulose materials such as wood powder, sawdust, wood shavings, flax fiber, old and useless newspaper, cotton spinning mill tankage, stalk, rice husk, corn cob, through pulverizes, sieve, one or more miscellany after the processing such as drying.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073778A (en) * | 2013-01-09 | 2013-05-01 | 上海大学 | Wood-plastic composite material and preparation method thereof |
| CN106188405A (en) * | 2016-08-19 | 2016-12-07 | 中国科学院化学研究所 | Graft modification super high molecular weight micronized polyethylene and solid phase grafting method thereof |
| CN107602975A (en) * | 2017-09-08 | 2018-01-19 | 芜湖市创源新材料有限公司 | A kind of polyethylene wood plastic clad plate of styrene acrylic Modification by Melt Grafting and preparation method thereof |
| CN111072857A (en) * | 2019-12-27 | 2020-04-28 | 无锡邰某人材料科技有限公司 | Compatilizer for polyolefin-based wood-plastic composite material and preparation method thereof |
| CN111875038A (en) * | 2020-07-29 | 2020-11-03 | 广东鹏清建设集团有限公司 | Biological net bed for treating black and odorous river and manufacturing method thereof |
| US11530281B2 (en) | 2016-08-19 | 2022-12-20 | Institute Of Chemistry, Chinese Academy Of Sciences | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
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| CN1986588A (en) * | 2006-12-04 | 2007-06-27 | 广州市鹿山化工材料有限公司 | Preparing process of solid phase grafted polyolefin wax copolymer |
| CN101456934A (en) * | 2009-01-04 | 2009-06-17 | 上海大学 | Method for preparing reactive interfacial compatibilizer |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103073778A (en) * | 2013-01-09 | 2013-05-01 | 上海大学 | Wood-plastic composite material and preparation method thereof |
| CN106188405A (en) * | 2016-08-19 | 2016-12-07 | 中国科学院化学研究所 | Graft modification super high molecular weight micronized polyethylene and solid phase grafting method thereof |
| CN106188405B (en) * | 2016-08-19 | 2019-02-15 | 中国科学院化学研究所 | Graft modification super high molecular weight micronized polyethylene and its solid phase grafting method |
| US11530281B2 (en) | 2016-08-19 | 2022-12-20 | Institute Of Chemistry, Chinese Academy Of Sciences | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
| CN107602975A (en) * | 2017-09-08 | 2018-01-19 | 芜湖市创源新材料有限公司 | A kind of polyethylene wood plastic clad plate of styrene acrylic Modification by Melt Grafting and preparation method thereof |
| CN111072857A (en) * | 2019-12-27 | 2020-04-28 | 无锡邰某人材料科技有限公司 | Compatilizer for polyolefin-based wood-plastic composite material and preparation method thereof |
| CN111875038A (en) * | 2020-07-29 | 2020-11-03 | 广东鹏清建设集团有限公司 | Biological net bed for treating black and odorous river and manufacturing method thereof |
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Application publication date: 20120926 |