CN106893268A - Modified terephtha-late composite of a kind of ramee and preparation method thereof - Google Patents
Modified terephtha-late composite of a kind of ramee and preparation method thereof Download PDFInfo
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- CN106893268A CN106893268A CN201510955453.4A CN201510955453A CN106893268A CN 106893268 A CN106893268 A CN 106893268A CN 201510955453 A CN201510955453 A CN 201510955453A CN 106893268 A CN106893268 A CN 106893268A
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- ramee
- whisker
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
The invention discloses modified polyadipate/butylene terephthalate composite of a kind of ramee and preparation method thereof.The component of composite is：100 parts, ramee 1-20 parts, whisker 5-10 parts, lubricant 0.5-2 parts, heat stabilizer 0.1-1 parts of polyadipate/butylene terephthalate.By the modified of the inventive method, the crystallization length of ramee is effectively reduced, improve its extension at break ability, meet the modified demand of polyadipate/butylene terephthalate；While enhancing polyadipate/butylene terephthalate material mechanical performance, production cost is also effectively reduced.
Description
Technical field
The present invention relates to a kind of terephtha-late composite, more particularly to a kind of modified benzene two of ramee
Formic acid fourth diester composite and preparation method thereof.
Background technology
Polyadipate/butylene terephthalate belongs to thermoplastic biodegradable's plastics, is tetramethylene adipate
With the copolymer of mutual-phenenyl two acid bromide two alcohol ester, the characteristic of PBA and PBT, existing preferable ductility are had concurrently
And elongation at break, also there are preferable heat resistance and impact property；Additionally, also there is excellent biological degradability,
It is that one of best degradable material is applied in very active and market during current biodegradable plastic is studied, in industry, agriculture
The fields such as industry, clothes, packaging have be widely applied very much.But, simple polyadipate/terephthalic acid (TPA)
Fourth diester has the shortcomings that tensile strength deficiency, high cost, it is necessary to modified in actual application.
The content of the invention
The present invention is a kind of modified phthalic acid fourth of ramee of solution above mentioned problem proposition of the prior art
Diester composite, including following component：
In order to optimize above-mentioned technical proposal, the technical measures that the present invention is taken also include：
Preferably, the number-average molecular weight of above-mentioned polyadipate/butylene terephthalate is 3.6 × 104。
Preferably, above-mentioned whisker is calcium sulfate crystal whiskers or magnesium sulfate crystal whisker.
Preferably, above-mentioned lubricant is zinc stearate or calcium stearate.
Preferably, above-mentioned heat stabilizer is maleic anhydride or epoxidized soybean oil.
On the other hand, the present invention also provides a kind of modified terephtha-late of above-mentioned ramee for preparing and is combined
The method of material, comprises the following steps：
Step one, ramee is pre-processed；
Step 2, whisker is pre-processed；
The crystalline substance that step 3, the ramee that the step one pretreatment is obtained and step 2 pretreatment are obtained
Must be placed in high speed blender together with polyadipate/butylene terephthalate, lubricant, heat stabilizer
Mixed；The modified terephtha-late composite of ramee is obtained.
In order to optimize above-mentioned preparation method, the technical measures that the present invention is taken also include：
Preprocessing process in above-mentioned steps one is preferably：It is 1~5% that ramee is immersed mass concentration respectively
Alkali lye in, 25 DEG C process 2~3h, through wash dealkalize, acid bath dealkalize, be washed to neutrality, dry after
Obtain pre-processing ramee.
It is highly preferred that ramee is immersed respectively when in the alkali lye that mass concentration is 1~5%, solid-liquid weight is mixed
Composition and division in a proportion is 1: 20.
Preprocessing process in above-mentioned steps two is preferably：Whisker is mixed with 50ml absolute ethyl alcohols, ultrasound point
Scattered 10min obtains finely dispersed suspension；By gamma-aminopropyl-triethoxy-silane coupling agent KH550 or metatitanic acid
One kind in ester coupling agent NZD-201 is dissolved in 50ml absolute ethyl alcohols；By unit for uniform suspension and coupling agent solution
It is well mixed in the 3h that flowed back at 80 DEG C；Room temperature is cooled to, is centrifuged, dried in 80 DEG C of vacuum drying ovens
To pretreatment whisker.
The present invention uses above-mentioned technical proposal, compared with prior art, have the following technical effect that：
Ramee has excellent hygroscopicity, gas permeability and antibacterial ability.But natural ramee and cotton
Fiber is compared, high with Young's modulus, and the degree of polymerization is big, and the characteristics of single fiber intensity is big, elastic force difference is not wear-resisting,
Crystallinity and the big shortcoming of the degree of orientation；By the modified of the inventive method, its crystallization length can be effectively reduced,
Its extension at break ability is improved, the modified demand of polyadipate/butylene terephthalate can be met.The present invention
Composite, ramee plays enhancing polyadipate/butylene terephthalate material power together with whisker
The effect of performance is learned, while effectively reducing cost.
Specific embodiment
The invention provides a kind of modified terephtha-late composite of ramee, including following component：
The present invention is described in more detail below by specific embodiment, for a better understanding of this hair
It is bright, but following embodiments are not intended to limit the scope of the invention.
Embodiment 1
In the present embodiment, calculate according to the mass fraction, composition and content are as follows：
Above-mentioned formula is reacted according to the following steps：
(1) immerse ramee respectively in the alkali lye that mass concentration is 4% first (solid-liquid Mixing ratio by weight 1:
20) 2h, is processed at 25 DEG C, through washing dealkalize, acid bath dealkalize, being washed to neutrality, ramie is obtained after drying
Fiber is standby.
(2) whisker is mixed with 50ml absolute ethyl alcohols, ultrasonic disperse 10min obtains finely dispersed suspension；
Gamma-aminopropyl-triethoxy-silane coupling agent (KH550) (by the 0.5% of whisker mass fraction) is dissolved in 50ml
Absolute ethyl alcohol；Unit for uniform suspension is well mixed in the 3h that flowed back at 80 DEG C with coupling agent solution；It is cooled to room temperature,
It is centrifuged, is dried in 80 DEG C of vacuum drying ovens
(3) by above-mentioned whisker, ramee and polyadipate/butylene terephthalate, lubricant, thermally-stabilised
Agent together, is placed in high speed blender and is mixed；
(4) above-mentioned well mixed raw material is placed in extruding pelletization in double screw extruder；
(5) above-mentioned composite particles are obtained standard testing batten through injection moulding.
(6) tensile strength, elongation at break is carried out to be measured.
Embodiment 2
In the present embodiment, calculate according to the mass fraction, composition and content are as follows：
Above-mentioned formula is reacted according to the following steps：
(1) sweet ramee is immersed into (solid-liquid Mixing ratio by weight in the alkali lye that mass concentration is 3% respectively first
1: 20), 3h is processed at 25 DEG C, through washing dealkalize, acid bath dealkalize, being washed to neutrality, obtained after drying
Ramee is standby.
(2) whisker is mixed with 50ml absolute ethyl alcohols, ultrasonic disperse 10min obtains finely dispersed suspension；
Titanate coupling agent NZD-201 (by the 0.5% of whisker mass fraction) is dissolved in 50ml absolute ethyl alcohols；Will
Unit for uniform suspension is well mixed in the 3h that flowed back at 80 DEG C with coupling agent solution；Room temperature is cooled to, is centrifuged,
Dried in 80 DEG C of vacuum drying ovens
(3) by above-mentioned whisker, ramee and polyadipate/butylene terephthalate, lubricant, thermally-stabilised
Agent together, is placed in high speed blender and is mixed；
(4) above-mentioned well mixed raw material is placed in extruding pelletization in double screw extruder；
(5) above-mentioned composite particles are obtained standard testing batten through injection moulding.
(6) tensile strength, elongation at break is carried out to be measured.
Embodiment 3
In the present embodiment, calculate according to the mass fraction, composition and content are as follows：
Above-mentioned formula is reacted according to the following steps：
(1) ramee is immersed (solid-liquid Mixing ratio by weight in the alkali lye that mass concentration is 2.5% respectively first
1: 20), 3h is processed at 25 DEG C, through washing dealkalize, acid bath dealkalize, being washed to neutrality, obtained after drying
Ramee is standby.
(2) whisker is mixed with 50ml absolute ethyl alcohols, ultrasonic disperse 10min obtains finely dispersed suspension；
Gamma-aminopropyl-triethoxy-silane coupling agent (KH550) (by the 0.5% of whisker mass fraction) is dissolved in 50ml
Absolute ethyl alcohol；Unit for uniform suspension is well mixed in the 3h that flowed back at 80 DEG C with coupling agent solution；It is cooled to room temperature,
It is centrifuged, is dried in 80 DEG C of vacuum drying ovens
(3) by above-mentioned whisker, ramee and polyadipate/butylene terephthalate, lubricant, thermally-stabilised
Agent together, is placed in high speed blender and is mixed；
(4) above-mentioned well mixed raw material is placed in extruding pelletization in double screw extruder；
(5) above-mentioned composite particles are obtained standard testing batten through injection moulding.
(6) tensile strength, elongation at break is carried out to be measured.
Embodiment 4
In the present embodiment, calculate according to the mass fraction, composition and content are as follows：
Above-mentioned formula is reacted according to the following steps：
(1) immerse ramee respectively in the alkali lye that mass concentration is 2% first (solid-liquid Mixing ratio by weight 1:
20) 3h, is processed at 25 DEG C, through washing dealkalize, acid bath dealkalize, being washed to neutrality, ramie is obtained after drying
Fiber is standby.
(2) whisker is mixed with 50ml absolute ethyl alcohols, ultrasonic disperse 10min obtains finely dispersed suspension；
Titanate coupling agent NZD-201 (by the 0.5% of whisker mass fraction) is dissolved in 50ml absolute ethyl alcohols；Will
Unit for uniform suspension is well mixed in the 3h that flowed back at 80 DEG C with coupling agent solution；Room temperature is cooled to, is centrifuged,
Dried in 80 DEG C of vacuum drying ovens
(3) by above-mentioned whisker, ramee and polyadipate/butylene terephthalate, lubricant, thermally-stabilised
Agent together, is placed in high speed blender and is mixed；
(4) above-mentioned well mixed raw material is placed in extruding pelletization in double screw extruder；
(5) above-mentioned composite particles are obtained standard testing batten through injection moulding.
(6) tensile strength, elongation at break is carried out to be measured.
Comparative example
With unmodified polyadipate/butylene terephthalate consumption/part as comparative example.
Using universal electrical tensile testing machine (SUN500 types are manufactured by Italian GALDABINI companies)
Above-described embodiment 1-4 and the final preparation-obtained sample tensile strength of comparative example, elongation at break are carried out
Determine, it the results are shown in Table shown in 1
Table 1
| Tensile strength/MPa | Elongation at break/% | |
| Embodiment 1 | 41.5 | 341.3 |
| Embodiment 2 | 36.4 | 323.6 |
| Embodiment 3 | 39.2 | 331.4 |
| Embodiment 4 | 29.0 | 309.6 |
| Comparative example | 22.1 | 321.0 |
As seen from the above table, the terephtha-late composite wood being modified using ramee via the method for the present invention
Material, tensile strength and Resisting fractre ability be significantly improved, not only enhancing polyadipate/terephthaldehyde
The mechanical property of the ester material of sour fourth two, while effectively reducing cost.
Specific embodiment of the invention has been described in detail above, but it is intended only as example, and the present invention is simultaneously
It is not restricted to particular embodiments described above.To those skilled in the art, it is any that the present invention is carried out
Equivalent modifications and substitute also all among scope of the invention.Therefore, spirit of the invention and model are not being departed from
Enclose lower made impartial conversion and change, all should be contained within the scope of the invention.
Claims (9)
1. the modified terephtha-late composite of a kind of ramee, it is characterised in that including following component：
2. composite according to claim 1, it is characterised in that described polyadipate/terephthalic acid (TPA)
The number-average molecular weight of fourth diester is 3.6 × 104。
3. composite according to claim 1, it is characterised in that described whisker be calcium sulfate crystal whiskers or
Magnesium sulfate crystal whisker.
4. composite according to claim 1, it is characterised in that described lubricant be zinc stearate or
Calcium stearate.
5. composite according to claim 1, it is characterised in that described heat stabilizer is maleic two
Acid anhydrides or epoxidized soybean oil.
6. a kind of modified terephtha-late of ramee prepared as described in claim 1-5 any one is combined
The method of material, it is characterised in that comprise the following steps：
Step one, ramee is pre-processed；
Step 2, whisker is pre-processed；
Step 3, the whisker that the step one ramee that obtains of pretreatment and step 2 pretreatment are obtained with
Together, being placed in high speed blender is carried out for polyadipate/butylene terephthalate, lubricant, heat stabilizer
Mixing；The modified terephtha-late composite of ramee is obtained.
7. method according to claim 6, it is characterised in that the preprocessing process in the step one is：
Ramee is immersed respectively in the alkali lye that mass concentration is 1~5%, 2~3h is processed at 25 DEG C, through washing
Dealkalize, acid bath dealkalize, neutrality is washed to, obtains pre-processing ramee after drying.
8. method according to claim 7, it is characterised in that ramee is immersed mass concentration respectively is
When in 1~5% alkali lye, solid-liquid Mixing ratio by weight is 1: 20.
9. method according to claim 6, it is characterised in that the preprocessing process in the step 2 is：
Whisker is mixed with 50ml absolute ethyl alcohols, ultrasonic disperse 10min obtains finely dispersed suspension；By γ-ammonia
One kind in propyl-triethoxysilicane coupling agent KH550 or titanate coupling agent NZD-201 is dissolved in 50ml
Absolute ethyl alcohol；Unit for uniform suspension is well mixed in the 3h that flowed back at 80 DEG C with coupling agent solution；It is cooled to room temperature,
It is centrifuged, drying obtains pre-processing whisker in 80 DEG C of vacuum drying ovens.
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| CN201510955453.4A CN106893268A (en) | 2015-12-17 | 2015-12-17 | Modified terephtha-late composite of a kind of ramee and preparation method thereof |
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Cited By (2)
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| CN109666267A (en) * | 2017-10-13 | 2019-04-23 | 上海东升新材料有限公司 | A kind of modified polyadipate/butylene terephthalate composite material and preparation method of palm leaf sheath fiber powder |
| CN113715238A (en) * | 2021-08-04 | 2021-11-30 | 哈尔滨化兴航卫航天生物科技有限公司 | Preparation method of biodegradable composite material |
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| CN113715238A (en) * | 2021-08-04 | 2021-11-30 | 哈尔滨化兴航卫航天生物科技有限公司 | Preparation method of biodegradable composite material |
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Application publication date: 20170627 |