CN104628966B - A kind of string strengthens environmentally friendly unsaturated polyester composite - Google Patents
A kind of string strengthens environmentally friendly unsaturated polyester composite Download PDFInfo
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- CN104628966B CN104628966B CN201510034264.3A CN201510034264A CN104628966B CN 104628966 B CN104628966 B CN 104628966B CN 201510034264 A CN201510034264 A CN 201510034264A CN 104628966 B CN104628966 B CN 104628966B
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- unsaturated polyester
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Abstract
The invention discloses a kind of string to strengthen environmentally friendly unsaturated polyester composite and preparation method thereof, using reactive solvents of the triethyleneglycol divinylether as solid unsaturated polyester (UP), and prepares composite by reinforcement of string.String, reactive solvents, solid strengthen environmentally friendly unsaturated polyester composite without styrene unsaturated polyester (UP) and initiator by the hot-forming string that obtains.Environmentally friendly unsaturated polyester (UP) used in composite prepared by the present invention is free of reactive solvents --- the styrene with carcinogenicity, with the characteristics of environment-friendly, cost is low, the composite of preparation has very high tensile strength, bending strength, bending modulus and impact strength.
Description
Technical field
The invention belongs to natural plant fibre reinforced resin technical field of composite materials, and in particular to a kind of string increases
Strong environmentally friendly unsaturated polyester composite and preparation method thereof.
Background technology
In recent years, the research for strengthening polymer composites using natural plant fibre receives extensive concern.Hemp is fine
Dimension has the advantages that yield is big, distribution is wide, intensity and modulus are high, is a kind of reinforcing material with broad prospect of application.Insatiable hunger
And polyester（UPE）It is the resin variety that dosage is maximum in galss fiber reinforced resin composite.UPE resins mechanical property with
Manufacturability is good, but largely uses volatile styrene as diluent and crosslinking agent in preparation process, the sky thus brought
Gas pollution problem has caused great concern.U.S. sanitaries in 2011 and public service administration are formally by styrene and inhalable glass
Fiber is classified as carcinogenic substance.Therefore, for fiber-reinforced resin matrix compound material industry, it is necessary to seek new reinforcement with as far as possible
Glass fibre usage amount is reduced, while takes measures to reduce the styrene dosage in prepared by composite.Both at home and abroad at present herein
The research of aspect mainly has：First, using polyurethane, melamine, phenolic resin etc. and UPE resin alloys, to reduce benzene second
Alkene usage amount and burst size, but the resin viscosity prepared is high, cost increase, and preparation technology is complicated；Second, added in UPE resins
Feature vegetable and animals oils reduce the usage amount of styrene, and modified vegetable and animals oils are easy by radical polymerization, cationic polymerization, open loop
The synthesizing new resins such as position polymerization, but building-up process still using vinyltoluene or bicyclopentadiene etc. as crosslinking agent and dilutes
The toxicity such as agent, vinyltoluene are bigger, and this resinoid mechanical property is relatively low；Third, UPE trees are used as using acrylic ester monomer
The reactive solvents of fat, but resin infiltration is low, viscosity is big, glass transition temperature and solidification rate are low, Compound Material Engineering
Performance degradation.UPE resins are prepared by raw material of vegetable and animals oils, it is significant to the usage amount of reduction petroleum-based products, still
Some petroleum-based mixtures must typically be added to obtain preferable performance, these material composition heat endurances are poor and lack
Participate in some active groups of resin solidification.Therefore, there has been no the root of the new UPE process for preparing resins without styrene at present
This solution.
The content of the invention
It is an object of the invention to provide a kind of string to strengthen environmentally friendly UPE composites and its preparation side
Method, the problems such as styrene usage amount is big, causes air pollution, is solved in traditional UPE resins.String prepared by the present invention increases
Strong environmentally friendly UPE composites have very high tensile strength, bending strength, bending modulus and impact strength.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of string strengthen environmentally friendly UPE composites be by string, environmentally friendly UPE resins and
Initiator is obtained by hot press forming technology；Described string is hemp；Described environmentally friendly UPE resins are
It is blended to obtain under certain condition with solid UPE using reactive solvents；Described initiator is peroxidized t-butyl perbenzoate.
The mass fraction of described composite raw material components is：80~100 parts of string, environmentally friendly UPE trees
80~100 parts of fat；3~7 parts of initiator.
The preparation process of described environmentally friendly UPE resins is：By 40~60 parts of solid UPE and reactive solvents 40
~60 parts are mixed to get environmentally friendly UPE resins under certain condition；Described solid UPE is that M-phthalic acid type is unsaturated
Polyester；Described reactive solvents are triethyleneglycol divinylether（English is entitled：Tri(ethylene glycol)
Divinyl ether, i.e. TDE）.
The specific preparation process that a kind of string as described above strengthens environmentally friendly UPE composites is as follows：
（1）String is placed at 100~105 DEG C and is dried to absolutely after shredding and being cut into the cm fibrofelts of 20 cm × 20
It is dry；
（2）It is standby that solid without 40~60 parts of styrene UPE is ground to 80~100 mesh powder；Reactive solvents 40~60
Part is placed in flask under 75 DEG C of water-baths heat after, be slowly added to solid without magnetic agitation after styrene unsaturated polyester (UP) powder extremely
It is completely dissolved；Taking-up is cooled to room temperature, that is, obtains environmentally friendly UPE resins；
（3）Weigh step（2）3~7 parts of mixing 2min of 80~100 parts of environmentally friendly UPE resins and initiator,
Produce environmentally friendly UPE resin mixture liquors；By 5~9 steps（1）String felt by orthogonal direction overlapping be arranged into fibre
Slab is tieed up, the rapid even application of resin mixture liquor on two surfaces of fibre mat, then move in punching block at 70 DEG C with 5~
7MPa pressure is cold-pressed 4~6min, resin penetration is entered in fibre mat；Then hot press be warming up to 150~170 DEG C 5~
20~40min of hot pressing under 7MPa pressure；30~90min of mould heat insulation pressurize after the completion of hot pressing, is allowed to naturally cool to room temperature.
The beneficial effects of the present invention are：The present invention using optimization combination of process parameters, string with it is environment-friendly
The amount ratio of type UPE resins（Mass ratio）For 1: 1,160 DEG C, hot pressing time 30min of hot pressing temperature, power can be prepared with mould pressing process
Learning the string of function admirable strengthens environmentally friendly UPE composites.Using environmentally friendly UPE as composite
Matrix, gained composite and traditional UPE resins（Using styrene as solvent）There is suitable stretching for the composite of matrix
Intensity, slightly lower bending strength and bending modulus, but there is higher impact strength.
Brief description of the drawings
Fig. 1 is the tensile strength of string/environmentally friendly UPE composites.Wherein, St-40 represents to use 40wt%
Styrene is the composite of UPE solvents；TDE-40 represents to use composites of the 40wt%TDE for UPE solvents；TDE-50 tables
Show and use composites of the 50wt%TDE for UPE solvents；St-40, TDE-40 and TDE-50 represent to contain in Fig. 2 and Fig. 3 abscissas
Justice is identical.Rectangular column upper and lower horizontal line represents the standard deviation of data mean value, block diagram expression two of the top without same letter in figure
Significant difference between group data, otherwise difference is not notable.
Fig. 2 is the bending property of string/environmentally friendly composite.
Fig. 3 is the impact strength of string/environmentally friendly composite.
Embodiment
Embodiment 1
Raw material：String is hemp（Hemp suede number is 130, average length 3cm）, purchased from Anhui copper
Mound Samsung Ma Ye Co., Ltds；Solid is without styrene unsaturated polyester (UP)（UPE）For M-phthalic acid type unsaturated polyester (UP), by the third two
Alcohol, M-phthalic acid and fumaric acid synthesize to obtain：Propane diols, M-phthalic acid and fumaric acid are purchased from the U.S.
Sigma-Aldrich companies；Reactive solvents are triethyleneglycol divinylether（TDE）, have purchased from Chinese medicines group chemical reagent
Limit company；Initiator is peroxidized t-butyl perbenzoate（TBPB）, purchased from Sigma-Aldrich（Shanghai）Trade Co., Ltd.
String strengthens environmentally friendly UPE composites：
By certain quality environmentally friendly UPE resins are obtained than hybrid solid without styrene UPE and reactive solvents.Will
String, environmentally friendly UPE resins and initiator are answered by the hot-forming environmentally friendly UPE of string enhancing that obtains
Condensation material.Reactive solvents are TDE, and the preparation process of environmentally friendly UPE resins is：Solid is ground without styrene UPE 60g
It is standby to be milled to 80~100 mesh powder；Reactive solvents TDE 40g are placed in flask under 75 DEG C of water-baths after heating, are slowly added to
Solid is completely dissolved to it without magnetic agitation after styrene UPE powder；Taking-up is cooled to room temperature, that is, obtains environmentally friendly UPE
Resin；The solid used, for M-phthalic acid type UPE, is closed without styrene UPE by propane diols, M-phthalic acid and fumaric acid
Into obtaining.
Composite material and preparation method thereof：String after shredding and being cut into the cm fibrofelts of 20 cm × 20, be placed in 100~
Over dry is dried at 105 DEG C；Weigh the environmentally friendly g of the UPE resins 75 and g of initiator 3.75 and mix 2min, obtain environment
Friendly UPE resin mixture liquors；By 5~9 string felts（75 g）Fibre mat is arranged into by orthogonal direction overlapping, tree
Then the rapid even application of fat mixed liquor is moved in punching block and is cold-pressed at 70 DEG C with 6MPa pressure on two surfaces of fibre mat
5min, resin penetration is set to enter in fibre mat；Then hot press is warming up to 160 DEG C of hot pressing 30min under 6MPa pressure；Hot pressing is complete
Into the heat-insulated pressurize 60min of rear mold, it is allowed to naturally cool to room temperature.
Reactive solvents and amount ratio of the solid without styrene UPE, it is 2 according to mass ratio in the preparation process：3；Plant
The amount ratio 1: 1 of fibres and environmentally friendly UPE resins；The dosage of initiator is the 5% of environmentally friendly UPE resin qualities.
Embodiment 2
Raw material：String is hemp（Hemp suede number is 130, average length 3cm）, purchased from Anhui copper
Mound Samsung Ma Ye Co., Ltds；Solid is without styrene unsaturated polyester (UP)（UPE）For M-phthalic acid type unsaturated polyester (UP), by the third two
Alcohol, M-phthalic acid and fumaric acid synthesize to obtain：Propane diols, M-phthalic acid and fumaric acid are purchased from the U.S.
Sigma-Aldrich companies；Reactive solvents are triethyleneglycol divinylether（TDE）, have purchased from Chinese medicines group chemical reagent
Limit company；Initiator is peroxidized t-butyl perbenzoate（TBPB）, purchased from Sigma-Aldrich（Shanghai）Trade Co., Ltd.
String strengthens environmentally friendly UPE composites：
By certain quality environmentally friendly UPE resins are obtained than hybrid solid without styrene UPE and reactive solvents.Will
String, environmentally friendly UPE resins and initiator are answered by the hot-forming environmentally friendly UPE of string enhancing that obtains
Condensation material.Reactive solvents are TDE, and the preparation process of environmentally friendly UPE resins is：Solid is ground without styrene UPE 50g
It is standby to be milled to 80~100 mesh powder；Reactive solvents TDE 50g are placed in flask under 75 DEG C of water-baths after heating, are slowly added to
Solid is completely dissolved to it without magnetic agitation after styrene UPE powder；Taking-up is cooled to room temperature, that is, obtains environmentally friendly UPE
Resin；The solid used, for M-phthalic acid type UPE, is closed without styrene UPE by propane diols, M-phthalic acid and fumaric acid
Into obtaining.
Composite material and preparation method thereof：String after shredding and being cut into the cm fibrofelts of 20 cm × 20, be placed in 100~
Over dry is dried at 105 DEG C；Weigh the environmentally friendly g of the UPE resins 75 and g of initiator 3.75 and mix 2min, obtain environment
Friendly UPE resin mixture liquors；By 5~9 string felts（75 g）Fibre mat is arranged into by orthogonal direction overlapping, tree
Then the rapid even application of fat mixed liquor is moved in punching block and is cold-pressed at 70 DEG C with 6MPa pressure on two surfaces of fibre mat
5min, resin penetration is set to enter in fibre mat；Then hot press is warming up to 160 DEG C of hot pressing 30min under 6MPa pressure；Hot pressing is complete
Into the heat-insulated pressurize 60min of rear mold, it is allowed to naturally cool to room temperature.
Reactive solvents and amount ratio of the solid without styrene UPE, it is 1 according to mass ratio in the preparation process：1；Plant
The amount ratio 1: 1 of fibres and environmentally friendly UPE resins；The dosage of initiator is the 5% of environmentally friendly UPE resin qualities.
Composite panel Mechanics Performance Testing：
Dumbbell shape sample is made in composite panel（Specification：Long 80mm, the wide 15mm in both ends, middle wide 10mm, gauge length 50mm,
Thickness 3mm）To test tensile property；The test sample of bending property is strip（Specification：60 mm×11 mm×3mm）；Punching
The test sample of hit intensity is strip（Specification：80 mm×10 mm×3mm）.Tensile strength test is according to ASTM D3039-
08 standard is carried out；Bending strength is carried out with modulus test according to ASTM D790-10 standards；Impact strength test is according to GB/
T1043-93.Tensile property and bending property test are completed on microcomputer controlled electronic universal tester, and impact strength test exists
Completed on balance weight impact testing machine.
The tensile strength of composite
Known by Fig. 1, with the resin composite materials that 40% styrene is UPE solvents（Tensile strength is 83.47MPa）Compare, adopt
There is suitable tensile strength with the resin composite materials that 40% and 50%TDE is UPE solvents, respectively 78.65MPa and
77.18MPa。
The bending strength of composite
Known by Fig. 2, the resin composite materials bending strength using 40% styrene, 40%TDE and 50%TDE as UPE solvents is distinguished
It is the resin composite materials bending strength of solvent compared with styrene using TDE for 139.27MPa, 122.46MPa and 109.80MPa
It is low for the resin composite materials of solvent.
The bending modulus of composite
Known by Fig. 2, the resin composite materials bending modulus using 40% styrene, 40%TDE and 50%TDE as UPE solvents is distinguished
It is the resin composite materials bending modulus of solvent compared with benzene second using TDE for 8738.40MPa, 7634.83MPa and 6885.66MPa
Alkene is low for the resin composite materials of solvent.
The impact strength of composite
Known by Fig. 3, the resin composite materials impact strength using 40% styrene, 40%TDE and 50%TDE as UPE solvents is distinguished
For 18.86kJ/m2、20.35kJ/m2And 21.64kJ/m2.Compared with styrene is the resin composite materials of solvent, using 40% He
50%TDE is that 7.9% and 14.7% is respectively increased in the resin composite materials impact strength of solvent.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (3)
1. a kind of string strengthens environmentally friendly unsaturated polyester composite, it is characterised in that：By following mass fraction
Raw material components be made：80~100 parts of string, 80~100 parts of environmentally friendly unsaturated polyester resin, initiator 3~7
Part；
Described environmentally friendly unsaturated polyester resin is made by the raw material components of following mass fraction：Solid without styrene not
40~60 parts of saturated polyester, 40~60 parts of reactive solvents；
Described string is hemp；Described environmentally friendly unsaturated polyester resin be using reactive solvents with
Solid obtains without styrene unsaturated polyester (UP) high-temperature blending；Described initiator is peroxidized t-butyl perbenzoate；
Described solid is M-phthalic acid type unsaturated polyester resin without styrene unsaturated polyester (UP)；Described reactive solvents
For triethyleneglycol divinylether.
2. string according to claim 1 strengthens environmentally friendly unsaturated polyester composite, it is characterised in that：
The preparation method of the environmentally friendly unsaturated polyester resin is：Solid is ground to 80 without styrene unsaturated polyester (UP)~
100 mesh powder；Reactive solvents heat in 75 DEG C of water-baths, are slowly added to solid without magnetic force after styrene unsaturated polyester (UP) powder
Stir to it and be completely dissolved；Taking-up is cooled to room temperature, produces environmentally friendly unsaturated polyester resin.
A kind of 3. side for preparing the environmentally friendly unsaturated polyester composite of string enhancing as claimed in claim 1
Method, it is characterised in that：Comprise the following steps that：
（1）String is placed at 100~105 DEG C after shredding and being cut into the cm fibrofelts of 20 cm × 20 and is dried to over dry；
（2）40~60 parts of solids are ground to 80~100 mesh powder without styrene unsaturated polyester (UP)；40~60 parts of reactive solvents
Heated in 75 DEG C of water-baths, be slowly added to solid and be completely dissolved without magnetic agitation after styrene unsaturated polyester (UP) powder to it；Take
Go out and be cooled to room temperature, that is, obtain environmentally friendly unsaturated polyester resin；
（3）Environmentally friendly unsaturated polyester resin and initiator are mixed into 2min, produced environmentally friendly unsaturated poly-
Ester resin mixture liquor；By 5~9 steps（1）String felt by orthogonal direction overlapping be arranged into fibre mat, resin is mixed
The rapid even application of liquid is closed on two surfaces of fibre mat, 4~6min is then cold-pressed with 5~7MPa pressure at 70 DEG C, made
Resin penetration enters in fibre mat；It is warming up to 150~170 DEG C of 20~40min of hot pressing under 5~7MPa pressure；Heat-insulated pressurize 30
~90min, and be allowed to naturally cool to room temperature.
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| CN105111478B (en) * | 2015-09-09 | 2017-11-21 | 福建农林大学 | A kind of epoxy monomer is modified bamboo fiber enhancing unsaturated polyester composite |
| CN105622858B (en) * | 2015-12-31 | 2020-11-03 | 华东理工大学华昌聚合物有限公司 | Synthesis method of environment-friendly styrene-free unsaturated polyester resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360863A (en) * | 1992-08-11 | 1994-11-01 | Bayer Aktiengesellschaft | Radiation curable compositions and their use |
| CN104262921A (en) * | 2014-09-18 | 2015-01-07 | 福建农林大学 | Bamboo fiber reinforced styrene-free unsaturated polyester composite material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360863A (en) * | 1992-08-11 | 1994-11-01 | Bayer Aktiengesellschaft | Radiation curable compositions and their use |
| CN104262921A (en) * | 2014-09-18 | 2015-01-07 | 福建农林大学 | Bamboo fiber reinforced styrene-free unsaturated polyester composite material and preparation method thereof |
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