CN106750782A - A kind of polyolefin enhancing composite and preparation method thereof - Google Patents
A kind of polyolefin enhancing composite and preparation method thereof Download PDFInfo
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- CN106750782A CN106750782A CN201611139168.6A CN201611139168A CN106750782A CN 106750782 A CN106750782 A CN 106750782A CN 201611139168 A CN201611139168 A CN 201611139168A CN 106750782 A CN106750782 A CN 106750782A
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- polyolefin
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- basalt fibre
- activator
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of polyolefin enhancing composite and preparation method thereof, composite of the present invention is prepared from including following weight portion raw material：1 25 parts of basalt fibre, 75 99 parts of polyolefin, 13 parts of coupling agent, 10 25 parts of activator；Contain barium phosphate in described basalt fibre；Described activator is inorganic acid that mass fraction is 3 5%；The composite property is excellent, is conducive to composite polyolefine material in the popularization and application of every field.
Description
Technical field
The present invention relates to composite polyolefine material field, and in particular to a kind of polyolefin strengthens composite and its preparation side
Method.
Background technology
Polyolefin is by alpha-olefins such as ethene, propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 4-methyl-1-pentenes
And some cycloolefins be polymerized alone or an analog thermoplastic resin obtained from combined polymerization general name, polyolefin have preferably it is comprehensive
Performance is closed, insulating properties, good corrosion resistance have good mechanical performance in temperature in use；But because ethylene linkage is with stronger
Reproducibility, causes polyolefin to there is resistance to elevated temperatures poor, wears no resistance, the defect such as loss of properties on aging, therefore, it is special at some
Under environment, polyolefin needs just be applied after carrying out the enhancing modification such as high temperature resistant, resistance to ag(e)ing.Now to polyolefin
Fiber-reinforced modified main use glass fiber material and carbon fibre material be modified treatment, modified effect significantly, but glass
Glass fiber and carbon fiber production cost is high, environmental pollution big, seriously limits the application of improved polyalkene.
Basalt fibre is a kind of emerging novel inorganic environment-friendly and green high performance fibre material, is following China's emphasis
One of four big high-performance fibers of development, it is aoxidized by silica, aluminum oxide, calcium oxide, iron oxide and titanium dioxide etc.
The basalt building stones of thing composition are prepared from after high-temperature fusion by spinning technique.Basalt continuous fiber is not only stablized
Property is good, but also with various excellent properties such as electrical insulating property, anticorrosive, flame resistant, high temperature resistant, and, basalt fibre
The discarded object that production technology is produced is few, and environmental pollution is small, directly can be transferred in ecological environment after product abandonment, without any danger
Evil, thus be a kind of qualified green, environment-friendly materials.
Therefore, glass is substituted using nontoxic, pollution-free, wide material sources, excellent performance, the basalt fiber material stablized
Glass fiber and carbon fiber strengthen polyolefine material, and polyolefin enhancing composite is that polyolefin enhancing is multiple obtained from
The new direction of condensation material development.But because basalt fibre is inorganic material, and polyolefin is macromolecule organic material, Liang Zhexiang
Capacitive extreme difference, and basalt fibre self structure and stable performance, fiber surface is smooth, surface-active site is few, causes the Black Warrior
Rock fiber is more difficult to carry out chemical bonding and mechanical riveted with polyolefine material in modifying process, i.e., basalt fibre is in polyene
It is to be individually present in hydrocarbon material, not good to polyolefine material enhancing effect, polyolefin strengthens the poor-performing of composite.
The content of the invention
It is an object of the invention to overcome polyolefin to strengthen the defect of composite property difference, there is provided a kind of polyolefin enhancing
Composite and preparation method thereof；Present invention basalt fibre of the selection containing barium phosphate as reinforcing material, in coupling agent and
Be coupled with polyolefin in the presence of activator, it is bonded, compound, so as to obtain basalt fibre and polyolefine material compatibility
More preferable polyolefine material is combined, and basalt fibre more preferably, makes the composite property more excellent polyolefin humidification, has
Beneficial to composite polyolefine material every field popularization and application.
In order to realize foregoing invention purpose, the invention provides a kind of polyolefin enhancing composite, including following weight
Part raw material are prepared from：1-25 parts of basalt fibre, 75-99 parts of polyolefin, 1-3 parts of coupling agent, 10-25 parts of work
Agent.
A kind of above-mentioned polyolefin enhancing composite, wherein it is described including short basalt fiber, it is basalt long fiber, profound
One kind in military rock cellucotton.
Wherein, barium phosphate is contained in described basalt fibre；Contain phosphate radical, phosphate radical and organic group in barium phosphate
Bonding capability it is strong, the polarity of basalt fibre and organic material can be reduced, increase and organic material compatibility；Preferably,
Described basalt fibre contains the barium phosphate of mass percent 0.1-2.0%；Most preferably, described basalt fibre contains
The barium phosphate of mass percent 0.3-0.8%.
Wherein, described polyolefin is polyethylene, polyvinyl chloride, polyvinyl alcohol, polypropylene, polystyrene, poly- methyl-prop
One kind in e pioic acid methyl ester.
Wherein, described coupling agent is methacryloxypropyl trimethoxy silane.
Wherein, described activator is that mass fraction is the hypochlorite of 3-5%；Described inorganic acid is sodium hypochlorite, secondary
One or more in potassium chlorate, calcium hypochlorite, barium hypochlorite.
Wherein, the polyolefin enhancing composite, also including auxiliary agent；The auxiliary agent includes dispersant, antiseptic, anti-quiet
One or more in electric agent, fire retardant, age resister, UV resistant agent；The species of the auxiliary agent can strengthen according to polyolefin
Composite requires to carry out specific aim adjustment addition in different application field.
Preferably, the polyolefin enhancing composite, including following weight portion raw material is prepared from：5-15 parts profound
The polyolefin of 85-95 parts of military rock fiber, 2-3 parts of coupling agent, 15-20 parts of activator.
A kind of polyolefin strengthens composite, and composite of the present invention is selected to contain and is easier bonded phosphorus with organic matrix
The basalt fibre of sour barium makes polyolefine material and basalt as reinforcing material, and in the presence of coupling agent and activator
Double bonded structures can be formed between fiber, bonded power is strong, phase separation is not likely to produce, so that basalt fibre and polyolefine material
Compatibility more preferably, basalt fiber is dramatically increased to the humidification of polyolefin, and the performance of resulting composite is also notable
Improve.
In order to realize foregoing invention purpose, further, the invention provides the system that a kind of polyolefin strengthens composite
Preparation Method, comprises the following steps：
（1）Pretreatment：Basalt fibre is carried out pre-processing to obtain treated basalt fiber with coupling agent and activator；
（2）It is compound：Treated basalt fiber and polyolefine material are carried out into Combined Processing, polyolefin enhancing composite is obtained.
A kind of above-mentioned polyolefin strengthens the preparation method of composite, and the temperature pre-processed wherein in step 1 is 50-70
DEG C, temperature is higher, and reaction speed is faster, but control is more difficult, and temperature is lower, and reaction speed is slower, and reaction effect is poorer；It is preferred that
, pretreatment temperature is 60-65 DEG C.
A kind of above-mentioned polyolefin strengthens the preparation method of composite, and the time pre-processed wherein in step 1 is 20-
40min, process time is more long, and process time better to basalt fibre surface treatment effect but long causes to process transition,
Basalt fiber performance is remarkably decreased, and is unfavorable for being modified the enhancing of polyolefin；Preferably, described pretreatment time is 25-
30min。
A kind of above-mentioned polyolefin strengthens the preparation method of composite, and the wherein Combined Processing in step 2 refers to by work
Skill means are chemically bonded basalt fibre is pre-processed with polyolefine material, basalt fibre is formed with polyolefine material
Unified overall method.
A kind of polyolefin strengthens the preparation method of composite, and preparation method of the present invention is first with barium phosphate in certain condition
Lower principle that can be bonded with organic group, by the pretreatment of coupling agent and activator, increases basalt fibre surface-active,
Increase the compatibility with polyolefin, then by Combined Processing, basalt fibre is carried out composite strengthening with polyolefin and obtain performance
More excellent polyolefin enhancing composite, the inventive method is simple, convenient, and being adapted to polyolefin strengthens the industry of composite
Change, large-scale production.
Compared with prior art, beneficial effects of the present invention：
1st, present invention enhancing composite is selected and contains the basalt fibre conduct that bonded barium phosphate is easier with organic matrix
Reinforcing material, the compatibility with polyolefin is good, and bonded power is strong, is not susceptible to be separated, and enhancing of the basalt fiber to polyolefin is made
With dramatically increasing, the performance of composite is significantly improved.
2nd, present invention enhancing composite is directed to Sexual behavior mode coupling agent and activator, basalt fibre is formed with polyolefin
Double bonded structures, the power that be combined with each other between basalt fibre and polyolefin is stronger, and the performance of composite is more preferable.
3rd, preparation method of the present invention, by the pretreatment to basalt fibre, increases basalt fibre surface-active, with
The compatibility of polyolefin increases, and the humidification to composite polyolefine material increases.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
For the scope of above-mentioned theme of the invention is only limitted to following embodiment, all technologies realized based on present invention belong to this
The scope of invention.
Embodiment 1
（1）Pretreatment：By the basalt fibre containing 0.3% barium phosphate of the 5 weight portions methacryloxy of 2 weight portions
The mass fraction of propyl trimethoxy silicane and 15 weight portions is that 3% sodium hypochlorite is pre-processed at a temperature of 60 DEG C
25min obtains treated basalt fiber；
（2）It is compound：The polythene material of treated basalt fiber and 95 weight portions is carried out into Combined Processing, polyolefin enhancing is obtained
Composite.
Embodiment 2
（1）Pretreatment：By the basalt fibre containing 0.8% barium phosphate of the 15 weight portions methacryloxy of 3 weight portions
The mass fraction of propyl trimethoxy silicane and 20 weight portions is that 5% postassium hypochlorite is pre-processed at a temperature of 50 DEG C
30min obtains treated basalt fiber；
（2）It is compound：The polythene material of treated basalt fiber and 85 weight portions is carried out into Combined Processing, polyolefin enhancing is obtained
Composite.
Embodiment 3
（1）Pretreatment：By the basalt fibre containing 2% barium phosphate of the 1 weight portion methacryloxy third of 1 weight portion
The mass fraction of base trimethoxy silane and 10 weight portions is that 3% barium hypochlorite carries out pretreatment 20min at a temperature of 65 DEG C
Obtain treated basalt fiber；
（2）It is compound：The polythene material of treated basalt fiber and 99 weight portions is carried out into Combined Processing, polyolefin enhancing is obtained
Composite.
Embodiment 4
（1）Pretreatment：By the basalt fibre containing 0.1% barium phosphate of the 25 weight portions methacryloxy of 3 weight portions
The mass fraction of propyl trimethoxy silicane and 25 weight portions is that 5% calcium hypochlorite is pre-processed at a temperature of 50 DEG C
40min obtains treated basalt fiber；
（2）It is compound：The polythene material of treated basalt fiber and 75 weight portions is carried out into Combined Processing, polyolefin enhancing is obtained
Composite.
Comparative example 1
（1）Pretreatment：By the basalt fibre of the 5 weight portions methacryloxypropyl trimethoxy silane of 2 weight portions
The pretreatment 25min basalt that must be modified is carried out at a temperature of 60 DEG C with the sodium hypochlorite that the mass fraction of 15 weight portions is 3% fine
Dimension；
（2）It is compound：The polythene material of treated basalt fiber and 95 weight portions is carried out into Combined Processing, polyolefin enhancing is obtained
Composite.
Comparative example 2
（1）Pretreatment：By the basalt fibre containing 0.3% barium phosphate of the 5 weight portions methacryloxy of 2 weight portions
Propyl trimethoxy silicane carries out pretreatment 25min at a temperature of 60 DEG C and obtains treated basalt fiber；
（2）It is compound：The polythene material of treated basalt fiber and 95 weight portions is carried out into Combined Processing, polyolefin enhancing is obtained
Composite.
Preparation-obtained polyethylene enhancing composite in above-described embodiment 1-4 and comparative example 1-3 is carried out into performance survey
Examination experimental record experimental result, record data is as follows：（Polyethylene：Tensile strength 14.5MPa, impact strength 6.8KJ/m2, highest
100 DEG C of temperature in use）
| Numbering | Polyolefin strengthens composite impact intensity（kJ/m2） | Polyolefin strengthens composite tensile strength（MPa） | Polyolefin strengthens composite maximum operation (service) temperature（℃） |
| Embodiment 1 | 12.9 | 23.2 | 125 |
| Embodiment 2 | 12.0 | 23.3 | 125 |
| Embodiment 3 | 12.5 | 23.1 | 125 |
| Embodiment 4 | 12.7 | 22.9 | 125 |
| Comparative example 1 | 8.2 | 17.3 | 115 |
| Comparative example 2 | 9.1 | 17.8 | 115 |
Above-mentioned analysis of experimental data is understood, the polyolefin prepared using technical solution of the present invention in embodiment 1-4 is strengthened
The notch impact strength of composite, tensile strength, maximum operation (service) temperature have and are obviously improved；And in the preparation method of comparative example 1
The basalt fibre of use does not contain barium phosphate, and fiber surface activity point position is few and active group is few after pretreatment, with polyolefin
Material compatibility is poor, the chemical bonding ability with polyolefine material, and polyolefin enhancing composite property is significantly reduced；Contrast
Activator is not used in the preparation method of example 2 to be pre-processed, it is impossible to which the barium phosphate to basalt fibre surface is activated, it is and poly-
The chemical bonding of olefin material is less able, and polyolefin enhancing composite property is significantly reduced.
Claims (10)
1. a kind of polyolefin strengthens composite, it is characterised in that be prepared from including following weight portion raw material：1-25 parts
Basalt fibre, 75-99 part of polyolefin, 1-3 parts of coupling agent, 10-25 parts of activator；
Contain barium phosphate in described basalt fibre；Described activator is that mass fraction is the hypochlorite of 3-5%.
2. composite according to claim 1, it is characterised in that described basalt fibre contains mass percent
The barium phosphate of 0.1-2.0%.
3. composite according to claim 2, it is characterised in that described basalt fibre contains mass percent
The barium phosphate of 0.3-0.8%.
4. composite according to claim 1, it is characterised in that described polyolefin is polyethylene, polyvinyl chloride, poly-
One kind in vinyl alcohol, polypropylene, polystyrene, polymethyl methacrylate.
5. composite according to claim 1, it is characterised in that described hypochlorite is sodium hypochlorite, hypochlorous acid
One or more in potassium, calcium hypochlorite, barium hypochlorite.
6. composite according to claim 1, it is characterised in that be prepared from including following weight portion raw material：5-
The polyolefin of basalt fibre 85-95 parts of 15 parts, 2-3 parts of coupling agent, 15-20 parts of activator.
7. the composite according to claim any one of 1-6, it is characterised in that also including auxiliary agent；The auxiliary agent includes
One or more in dispersant, antiseptic, antistatic additive, fire retardant, age resister, UV resistant agent.
8. a kind of polyolefin strengthens the preparation method of composite, it is characterised in that comprise the following steps：
（1）Pretreatment：Basalt fibre is carried out pre-processing to obtain treated basalt fiber with coupling agent and activator；
（2）It is compound：Treated basalt fiber and polyolefine material are carried out into Combined Processing, polyolefin enhancing composite is obtained.
9. preparation method according to claim 8, it is characterised in that the temperature pre-processed in step 1 is 50-70 DEG C, in advance
The time for the treatment of is 20-40min.
10. preparation method according to claim 8, it is characterised in that the temperature pre-processed in step 1 is 60-65 DEG C, in advance
The time for the treatment of is 25-30min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107705898A (en) * | 2017-10-31 | 2018-02-16 | 四川力智久创知识产权运营有限公司 | A kind of tension PE cable |
| CN107705897A (en) * | 2017-10-31 | 2018-02-16 | 四川力智久创知识产权运营有限公司 | A kind of tension polystyrene cable |
| CN107833670A (en) * | 2017-09-30 | 2018-03-23 | 四川力智久创知识产权运营有限公司 | A kind of high mechanical properties insulated cable |
| CN107919190A (en) * | 2017-10-31 | 2018-04-17 | 四川力智久创知识产权运营有限公司 | A kind of tension polyvinyl chloride cable |
| CN107945959A (en) * | 2017-10-31 | 2018-04-20 | 四川力智久创知识产权运营有限公司 | A kind of modified polyvinyl chloride wear-resistant cable |
| CN107945913A (en) * | 2017-10-31 | 2018-04-20 | 四川力智久创知识产权运营有限公司 | A kind of EP rubbers wear-resistant cable |
| CN117209874A (en) * | 2023-09-18 | 2023-12-12 | 四川亚塑新材料有限公司 | Basalt fiber reinforced composite material and preparation method and application thereof |
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| CN101906250A (en) * | 2010-08-13 | 2010-12-08 | 东南大学 | Basalt fiber reinforced wood-plastic composite material and preparation method thereof |
| CN103044803A (en) * | 2012-12-07 | 2013-04-17 | 广东工业大学 | Method for preparing sound absorption and sound insulation composite material |
| CN104356511A (en) * | 2014-11-26 | 2015-02-18 | 朱建一 | High-rigidity creep-resistant long-fiber-reinforced master batch for wood plastic products, and preparation and mold thereof |
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| CN101906250A (en) * | 2010-08-13 | 2010-12-08 | 东南大学 | Basalt fiber reinforced wood-plastic composite material and preparation method thereof |
| CN103044803A (en) * | 2012-12-07 | 2013-04-17 | 广东工业大学 | Method for preparing sound absorption and sound insulation composite material |
| CN104356511A (en) * | 2014-11-26 | 2015-02-18 | 朱建一 | High-rigidity creep-resistant long-fiber-reinforced master batch for wood plastic products, and preparation and mold thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107833670A (en) * | 2017-09-30 | 2018-03-23 | 四川力智久创知识产权运营有限公司 | A kind of high mechanical properties insulated cable |
| CN107705898A (en) * | 2017-10-31 | 2018-02-16 | 四川力智久创知识产权运营有限公司 | A kind of tension PE cable |
| CN107705897A (en) * | 2017-10-31 | 2018-02-16 | 四川力智久创知识产权运营有限公司 | A kind of tension polystyrene cable |
| CN107919190A (en) * | 2017-10-31 | 2018-04-17 | 四川力智久创知识产权运营有限公司 | A kind of tension polyvinyl chloride cable |
| CN107945959A (en) * | 2017-10-31 | 2018-04-20 | 四川力智久创知识产权运营有限公司 | A kind of modified polyvinyl chloride wear-resistant cable |
| CN107945913A (en) * | 2017-10-31 | 2018-04-20 | 四川力智久创知识产权运营有限公司 | A kind of EP rubbers wear-resistant cable |
| CN117209874A (en) * | 2023-09-18 | 2023-12-12 | 四川亚塑新材料有限公司 | Basalt fiber reinforced composite material and preparation method and application thereof |
| CN117209874B (en) * | 2023-09-18 | 2024-04-30 | 四川亚塑新材料有限公司 | Basalt fiber reinforced composite material and preparation method and application thereof |
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Application publication date: 20170531 |