CN106366598B - The material for preparing the method for fiber reinforcement poly-lactic acid material and being prepared by this method - Google Patents
The material for preparing the method for fiber reinforcement poly-lactic acid material and being prepared by this method Download PDFInfo
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- CN106366598B CN106366598B CN201610922081.XA CN201610922081A CN106366598B CN 106366598 B CN106366598 B CN 106366598B CN 201610922081 A CN201610922081 A CN 201610922081A CN 106366598 B CN106366598 B CN 106366598B
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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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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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Abstract
This disclosure relates to a kind of method for preparing fiber reinforcement poly-lactic acid material and the fiber reinforcement poly-lactic acid material prepared by this method, method includes the following steps: S1, polylactic acid is subjected to melt process, the polylactic acid material after being melted；S2, the fibrous material by coupling agent, thermosetting resin and curing agent roller coating after fiber surface obtains roller coating；S3, it is squeezed out after the polylactic acid material after the melting is blended with the fibrous material after the roller coating in screw extruder.The more traditional poly-lactic acid material of fiber reinforcement poly-lactic acid material prepared by this method solves agglomeration traits and material mixture ratio instability problem caused by fiber winding, and fiber and poly-lactic acid material attachment force are stronger, material mechanical performance is higher.
Description
Technical field
This disclosure relates to degradation material production field, and in particular, to a kind of fiber reinforcement poly-lactic acid material of preparing
Method and the material prepared by this method.
Background technique
PLA Chinese is polylactic acid, and being take lactic acid as the obtained polymer of main polymerizable raw material, and PLA material can be by
Biodegrade is ideal Green Polymer Material, therefore is the excellent substitute products of traditional petrochemical industry plastics.It is general in the prior art
All over the mechanical performance for improving PLA material using fibre-reinforced method.
Fiber reinforcement PLA material generally takes extruding pelletization to be processed at present, and there are mainly three types of feeding manners: first
Kind is that blender is added and is blended, then passes through spout and feeds by after substrate, fiber and the weighing of various auxiliary agents；Second
It is to weigh substrate, fiber and auxiliary agent again by arrow, is separately added into spout charging further according to weight/power ratio；The third
It is to feed substrate and auxiliary agent by spout, fiber is fed by side spout；
The first is only applicable to the addition of chopped strand material with second of feeding manner, can not add continuous fiber, the
Three kinds of modes are added suitable for continuous fiber material, but plant fiber and substrate plyability are poor, in screw rod shearing Blending Processes
Wound upon themselves easily occur and reunite, cause material system proportion unstable, or even blocking head causes normally to produce.
It is therefore desirable to be improved to existing fiber reinforcement PLA material processing technology, to reduce fiber in system
Agglomeration traits caused by winding curling, provide that a kind of material system proportion is stablized, fiber and poly-lactic acid material attachment force are strong, material
Expect the high fiber reinforcement PLA material of mechanical performance.
Summary of the invention
The purpose of the disclosure is to overcome drawbacks described above present in existing fiber reinforcement PLA material processing technology, is provided
A kind of material system proportion stablizes, fiber and polylactic acid attachment force is strong, the mechanical property of materials is high fiber reinforcement PLA material and its
Preparation method.
To achieve the above object, disclosure first aspect: providing a kind of method for preparing fiber reinforcement poly-lactic acid material, packet
Include following steps:
S1, polylactic acid is subjected to melt process, the polylactic acid material after being melted；
S2, the fibrous material by coupling agent, thermosetting resin and curing agent roller coating after fiber surface obtains roller coating；
S3, after the polylactic acid material after the melting is blended with the fibrous material after the roller coating in screw extruder
It squeezes out.
Preferably, in step S2, by the coupling agent, the thermosetting resin and the curing agent, successively successively roller coating exists
The surface of the fiber.
Preferably, by weight, the dosage of the polylactic acid is 73-86 parts, the dosage of the fiber is 10-20 parts,
The dosage of the coupling agent is 0.196-0.204 parts, and the dosage of the thermosetting resin is 2-3 parts, the dosage of the curing agent
It is 0.098-0.102 parts.
Preferably, the fiber is continuous plant fiber, and the diameter of the continuous plant fiber is 15-35 μm.
Preferably, the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy
At least one of base silane and γ-(methacryloxypropyl) propyl trimethoxy silicane；The thermosetting resin is unsaturation
At least one of polyester, epoxy resin and polyurethane；The curing agent be di-tert-butyl peroxide, cyclohexanone peroxide and
At least one of benzoyl peroxide.
Preferably, in step S3, the condition being blended in the screw extruder includes: that temperature is 180-210 DEG C.
Preferably, the weight average molecular weight of the polylactic acid is 100000-250000.
Preferably, in step S1, mixture is obtained again to mixture progress after polylactic acid first to be contacted to mixing with toughener
Melt process melted after polylactic acid material.
Preferably, the polylactic acid relative to 100 parts by weight, the dosage of the toughener are 1-5 parts by weight；The toughener
For olefin copolymer.
Optionally, the toughener is the block copolymerization of vinyl-vinyl acetate copolymer and/or styrene and butadiene
Object.
Disclosure second aspect: providing a kind of fiber reinforcement poly-lactic acid material, which is by this
What the method for open first aspect was prepared.
Through the above technical solutions, the more traditional poly- cream of fiber reinforcement poly-lactic acid material prepared by the method that the disclosure provides
Sour material solves agglomeration traits caused by fiber winding and material mixture ratio instability problem, fiber are connect with poly-lactic acid material
Power is stronger, the mechanical property of materials is higher.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
Disclosure first aspect: providing a kind of method for preparing fiber reinforcement poly-lactic acid material, and this method includes following step
It is rapid: polylactic acid S1, to be subjected to melt process, the polylactic acid material after being melted；S2, by coupling agent, thermosetting resin and solid
Fibrous material of the agent roller coating after fiber surface obtains roller coating；S3, in screw extruder by the polylactic acid after the melting
Material squeezes out after being blended with the fibrous material after the roller coating.
Wherein, the weight average molecular weight of the polylactic acid can change in very large range, for example, the weight of the polylactic acid is equal
Molecular weight can be 100000-250000.
According to the disclosure in a first aspect, polylactic acid can be contacted with toughener and/or stabilizer mixing after mixed
It closes object and the polylactic acid material after melt process is melted is carried out to mixture again, it is preferable mechanical that this can be such that polylactic acid has
Performance and heat resistance.The adding method of the toughener and/or stabilizer can be the conventional method of this field.Relative to
The polylactic acid of 100 parts by weight, the dosage of the toughener are 1-5 parts by weight.The type of the toughener can be selected from this field
Conventional use of toughener type, for example, being olefin copolymer, optionally, toughener is vinyl-vinyl acetate copolymer
(EVA) and/or the block copolymer (SBS) of styrene and butadiene, described in a kind of preferred embodiment of the disclosure
Toughener is olefin copolymer, and the dosage of toughener is 3 parts by weight.
According to the disclosure in a first aspect, the condition of melt process described in step a can be those skilled in the art institute
It is well known, for example, it is 180-210 DEG C that the condition of melt process described in step a, which includes: temperature,.
According to the disclosure in a first aspect, in order to avoid fiber winds agglomeration traits caused by curling, step in system
In rapid S2, by the fibrous material of coupling agent, thermosetting resin and curing agent roller coating after fiber surface obtains roller coating.In order to improve
The attachment force of fiber and thermosetting resin, first in fiber surface roller coating coupling agent, then roller coating thermosetting resin again.Curing agent
Effect be to solidify thermosetting resin in fiber surface, therefore the last roller coating for carrying out curing agent.By the coupling agent, institute
Stating thermosetting resin and the curing agent, successively successively roller coating is during the fiber surface, for the time of roller coating operation
Interval is not particularly limited, and the control of time interval can be carried out by controlling the conveying speed of fiber, for example, roller coating is coupled
The time interval of agent and roller coating thermosetting resin can be 1-3s, and the time interval of roller coating thermosetting resin and roller coating curing agent can
Think 1-3s.By the fibrous material after the roller coating and the poly- cream after the melting in 2s after the roller coating operation for carrying out curing agent
Sour material is blended.The disclosure is not particularly limited the temperature of roller coating in step S2, can 15-30 DEG C at a temperature of into
Row.
According to the disclosure in a first aspect, the fiber is continuous plant fiber, and the diameter of the continuous plant fiber
It is 15-35 μm.The continuous plant fiber can be to be had by vegetable materials such as bamboo, fiber crops using what spinning process prepared
The plant fiber of certain mechanical strength and naturally biodegradable characteristic.Wherein, by weight, the dosage of the polylactic acid is 73-
86 parts, the dosage of the fiber be 10-20 part, the dosage of the coupling agent is 0.196-0.204 parts, the thermosetting resin
Dosage is 2-3 parts, and the dosage of the curing agent is 0.098-0.102 parts.The coupling agent can by this field routine use
, the coupling agent can be silane coupling agent, for example, the coupling agent be gamma-aminopropyl-triethoxy-silane (KH550),
γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane (KH560) and γ-(methacryloxypropyl) propyl trimethoxy silicane
At least one of (KH570)；The thermosetting resin can be conventional use of for this field, and the thermosetting resin is not
At least one of saturated polyester, epoxy resin and polyurethane；The curing agent can be conventional use of for this field, example
Such as, the curing agent is at least one of di-tert-butyl peroxide, cyclohexanone peroxide and benzoyl peroxide.
According to the disclosure in a first aspect, in step S3, the condition being blended in the screw extruder includes: that temperature is
180-210℃.Under this condition, thermosetting resin can solidify rapidly, so that fiber is changed into rigidity from flexible state
State, and then be easy to produce fracture under the shearing of screw rod, avoid the agglomeration traits caused by fiber winding curling, fracture
Rear fiber may be implemented to be sufficiently mixed with polylactic acid, so that material system proportion is stablized.
According to the disclosure in a first aspect, the screw extruder can be the conventional use of parallel dual-screw in this field
Extruder.Fibrous material after the roller coating can be imported by the extrusion middle section side spout of screw extruder, polylactic acid or
The mixture of polylactic acid and toughener can be imported by the main spout of screw extruder.Polylactic acid or polylactic acid and toughener
Polylactic acid material of the mixture after melted by heating is melted in screw extruder.Polylactic acid material after the melting with
The process that fibrous material after the roller coating is blended can be carried out in the polymer solids conveying section of screw extruder.Extruder
Screw speed can be 400-800r/min.
The second aspect of the disclosure: providing a kind of fiber reinforcement poly-lactic acid material, the fiber reinforcement poly-lactic acid material be by
What the method for disclosure first aspect was prepared.The density of poly-lactic acid material provided by disclosure second aspect is no more than
1.28g/cm3；Tensile strength can reach 15.1MPa or more, and bending strength can reach 16.6MPa or more, and notch impact strength can
Reach 7.7kJ/m2More than, vicat softening temperature can reach 88 DEG C.
The disclosure is further illustrated by the following examples, but therefore the disclosure is not any way limited.
In embodiment and comparative example, the regulation of the test method of density referring to ISO 1183-1A, tensile strength and stretching die
Regulation of the test method of amount referring to ISO 527-2, regulation of the test method of bending strength referring to ISO 178, notch shock
Regulation of the test method of intensity referring to ISO 179-1/1eA, the rule of the test method reference ISO 306 of vicat softening temperature
It is fixed.
Screw extruder used by embodiment and comparative example is the SK36 type screw extruder of Nanjing Ke Ya company production.
Embodiment 1-3
By polylactic acid, (purchased from NatureWorks company, the trade mark is each parts by weight of raw materials formula listed according to table 1
4032D, weight average molecular weight 150000-180000) (ethylenic copolymer, is purchased from E.I.Du Pont Company, and the trade mark is with toughener
Biomax Strong 100) mixing, melt process is carried out in the first spiro rod section of screw extruder, temperature is 180 DEG C, is obtained
Polylactic acid material after melting；
Continuous plant fiber is taken (to be purchased from Weifang Hao Fang Textile Co., Ltd., fiber grade: middle spy's yarn, fibre diameter 15-35
μm), roller coating processing is carried out to the continuous plant fiber, the coupling agent of roller coating is silane coupling agent gamma-aminopropyl-triethoxy
Silane (is purchased from Nanjing Quan Xi Chemical Co., Ltd., trade mark KH-550), and the thermosetting resin of roller coating is that unsaturated polyester (UP) (is purchased from
Tianjin He Cai resin Co., Ltd, trade mark 182#), the curing agent of roller coating is that di-tert-butyl peroxide (is purchased from the vast think of in Shanghai
Chemical Co., Ltd.).Roller coating carries out at 25 DEG C, and coupling agent roller coating is obtained the first roller coating material on the surface of plant continuous fiber
Expect, thermosetting resin roller coating is obtained into the second roller coating material in the first roller coating material surface after 2s, curing agent roller coating exists after 2s
Second roller coating material surface obtains the fibrous material after roller coating, and the fibrous material after roller coating, which is directed into extruder entrance, in 2s makes
It enters in screw rod is blended at 200 DEG C with the polylactic acid material after melting.Pelletizing is squeezed out after blending obtains material 1-3.Screw rod
The screw speed of extruder is 650r/min.
Density, tensile strength, bending strength, notch impact strength and the Wei Ka of detection gained fiber reinforcement poly-lactic acid material
Softening temperature, testing result are shown in Table 2.
Table 1
Embodiment 4
Fiber reinforcement poly-lactic acid material is prepared according to the method for embodiment 1, unlike, toughener is not added, material is obtained
Material 4.Density, tensile strength, bending strength, notch impact strength and the Wei Ka softening of detection gained fiber reinforcement poly-lactic acid material
Temperature, testing result are shown in Table 2.
Embodiment 5
Fiber reinforcement poly-lactic acid material is prepared according to the method for embodiment 1, unlike, unsaturated polyester (UP) is replaced with into ring
Oxygen resin obtains material 5.Density, tensile strength, the bending strength, notch shock of detection gained fiber reinforcement poly-lactic acid material
Intensity and vicat softening temperature, testing result are shown in Table 2.
Embodiment 6
Fiber reinforcement poly-lactic acid material is prepared according to the method for embodiment 1, unlike, toughener is replaced with into ethylene-
Vinyl acetate copolymer (EVA), obtains material 6.It is the detection gained density of fiber reinforcement poly-lactic acid material, tensile strength, curved
Qu Qiangdu, notch impact strength and vicat softening temperature, testing result are shown in Table 2.
Comparative example 1
Fiber reinforcement poly-lactic acid material is prepared according to the method for embodiment 1, unlike, coupling agent is not added, material is obtained
Expect D1.Density, tensile strength, bending strength, notch impact strength and the Wei Ka for detecting gained fiber reinforcement poly-lactic acid material are soft
Change temperature, testing result is shown in Table 2.
Comparative example 2
Fiber reinforcement poly-lactic acid material is prepared according to the method for embodiment 1, unlike, thermosetting resin is not added and is consolidated
Agent obtains material D2.The density of detection gained fiber reinforcement poly-lactic acid material, tensile strength, bending strength, notch shock are strong
Degree and vicat softening temperature, testing result are shown in Table 2.
Table 2
It is more traditional to can be seen that fiber reinforcement poly-lactic acid material prepared by the method that the disclosure provides from the data of table 2
Poly-lactic acid material solves agglomeration traits and material mixture ratio instability problem caused by fiber winding, so that fiber and polylactic acid
Material attachment force is stronger, the mechanical property of materials is higher.
When without coupling agent or without thermosetting resin and curing agent it can be seen from the comparison of embodiment and comparative example
When, prepared fiber reinforcement poly-lactic acid material is since the winding reunion of fiber causes material mixture ratio unstable, the items of material
Mechanical property especially shock resistance is poor.
Also, it is preferred that coupling agent is Silane coupling agent KH550, thermosetting resin is unsaturated polyester (UP) and curing agent is
Under conditions of di-tert-butyl peroxide, the vicat softening temperature of material is higher and every mechanical property is higher.
It is preferred that the shock resistance of material is higher under conditions of adding toughener.
The preferred embodiment of the disclosure is described in detail above, still, during the disclosure is not limited to the above embodiment
Detail a variety of simple variants can be carried out to the technical solution of the disclosure in the range of the technology design of the disclosure, this
A little simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (10)
1. a kind of method for preparing fiber reinforcement poly-lactic acid material, which comprises the following steps:
S1, polylactic acid is subjected to melt process, the polylactic acid material after being melted；
S2, by coupling agent, thermosetting resin and curing agent successively successively roller coating fiber surface obtain roller coating after fibrous material；
The fiber is continuous plant fiber；The thermosetting resin is unsaturated polyester (UP)；The curing agent is di-tert-butyl peroxide
Object；
S3, it is squeezed after the polylactic acid material after the melting is blended with the fibrous material after the roller coating in screw extruder
Out.
2. according to the method described in claim 1, wherein, by weight, the dosage of the polylactic acid is 73-86 parts, described
The dosage of fiber is 10-20 parts, and the dosage of the coupling agent is 0.196-0.204 parts, and the dosage of the thermosetting resin is 2-3
Part, the dosage of the curing agent is 0.098-0.102 parts.
3. according to the method described in claim 2, wherein, the diameter of the continuous plant fiber is 15-35 μm.
4. method according to claim 1 or 3, wherein the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-
At least one in (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and γ-(methacryloxypropyl) propyl trimethoxy silicane
Kind.
5. according to the method described in claim 4, wherein, in step S3, the condition being blended in the screw extruder includes:
Temperature is 180-210 DEG C.
6. method according to claim 1 or 3, wherein the weight average molecular weight of the polylactic acid is 100000-250000.
7. according to the method described in claim 6, wherein, in step S1, being obtained after polylactic acid first to be contacted to mixing with toughener
Mixture carries out the polylactic acid material after melt process is melted to mixture again.
8. according to the method described in claim 7, wherein, relative to the polylactic acid of 100 parts by weight, the dosage of the toughener is
1-5 parts by weight；The toughener is olefin copolymer.
9. according to the method described in claim 8, wherein, the toughener is vinyl-vinyl acetate copolymer and/or benzene second
The block copolymer of alkene and butadiene.
10. a kind of fiber reinforcement poly-lactic acid material, which is characterized in that the fiber reinforcement poly-lactic acid material is by claim 1-9
Any one of described in method be prepared.
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