CN1872913A - Method for preparing polycondensation reaction type reinforced thermoplastic resin in long fibres - Google Patents
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Abstract
This invention relates to a method for manufacturing long-fiber-reinforced thermoplastic resin by condensation polymerization. The method comprises: (1) performing esterification or interesterification on the raw material to form esterified material; (2) performing melt-condensation polymerization to obtain low-viscosity condensation polymer, and introducing the molten condensation polymer into a dip tank; (3) preheating fiber bundles, and passing through the inside of the dip tank so that the molten condensation polymer adhere to the surface of the fibers to form predipped material; (4) cooling and cutting to obtain low-viscosity chips; (5) performing solid phase condensation polymerization to obtain the final product. The method can integrate esterification (interesterification), condensation polymerization, dipping and solid phase condensation polymerization, thus can utilize present equipment to manufacture long-fiber-reinforced thermoplastic resin, such as PET, PTT, PBT and PEN.
Description
Technical field
The present invention relates to the preparation of macrofiber reinforced composite, relate in particular to the preparation of fiber reinforced thermoplastic resin, be in particular a kind of preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres, belong to the synthetic and processing technique field of macromolecular material.
Background technology
Since nineteen fifty-one R.Bradit adopted styrafil to make matrix material first, people deepened continuously for the research of matrix resin, strongthener and the forming method of fiber reinforced thermolplastic composite material (FRTP).The plurality of advantages of this material, good as toughness height, impact resistance, be not subjected to the period of storage restriction, the manufacturing cycle is short, prepreg is stable, chemical resistance is good, rate of moisture absorption is low, can repeat processing etc., be familiar with and utilize by people, its output and Application Areas constantly enlarge, and now are used widely in industries such as automobile, electronics, electrical equipment, medicine, building materials.
According to the geometrical dimension of fortifying fibre, FRTP can be divided into: long fiber reinforced thermoplastic composites (LFRTP) and staple fibre strengthen thermoplastic composite (SFRTP).Than SFRTP, LFRTP has higher rigidity (stiffness) and better toughness (fracture toughness), and the resistance toheat of material also improves a lot.So people attach great importance to the development research of LFRTP and material resin thereof in recent years.
In the prior art, prepare the most frequently used method of fiber-reinforced thermoplastic resin and be to use screw extrusion press, it is also extruded fortifying fibre when the thermoplastic resin melting is extruded, just obtains fiber-reinforced thermoplastic resin behind the granulating and forming.In the middle of this process, the shearing action of extruder screw will cause damage even staple fiber to fiber, and generally in 0.3～0.5mm scope, this has just reduced the performance of fiber as strongthener to staple length in the middle of the resin of acquisition.In addition, screw rod is extruded needs high-temperature operation, and the melt viscosity of resin is very big, is difficult to impregnation of fibers, and the bond effect between resin and the fiber is not ideal enough.
Can in resin, obtain the technical essential of good dipping at fiber, carried out big quantity research both at home and abroad, multiple technologies of preparing such as melt impregnation, suspension dipping, powder preimpregnation, fiber hybrid, in-situ polymerization and film inlaying have mainly been developed, as U.S. Pat 4640861, US4828776, patent of Institute of Chemistry, Academia Sinica " a kind of glass-fiber-reinforced polyester (PET) matrix material and preparation method thereof " (ZL 95104996.8) or the like.
In the melt impregnation method, adopt low viscosity polymer monomer and oligopolymer impregnation of fibers thereof, and then make LFRTP through polymerization, molding procedure, can fundamentally solve the dipping problem between above-mentioned resin and the fiber, thereby obtain comparatively ideal matrix material.At present, have the patent report of this respect both at home and abroad, but polymkeric substance that their are suitable for is comparatively special, perhaps its method itself has open defect.
For example, U.S. Pat 5891560 discloses a kind of long fiber reinforced thermoplastic composites, and its preparation raw material is very special, is a kind of not only can at high temperature the degraded but also polymeric urethane at low temperatures, and the viscosity of prepared resin can not be regulated; U.S. Pat 5935508 and European patent EP 0290849 disclose the photopolymerization continuous fiber reinforced thermoplastic composite material that causes with UV-light, but the penetrativity of UV-light is limited, are difficult to the thicker goods of preparation by this method.
Jieshijie Novel Materials Co., Ltd, Shanghai's invention disclosed patent " manufacture method of continuous fiber intensified response type resin " (number of patent application: 01145281.1), the olefin monomer that adopts free redical polymerization obtains the response type continuous fiber and strengthens resin through microwave radiation polymerization, curing molding after the cooling.This method can make bonding degree long fibre reinforced thermoplastic resin based composite material preferably, but only is applicable to that preparation can carry out the polyolefins thermoplastic matrix material of radical polymerization.
Summary of the invention
A kind of preparation method who the purpose of this invention is to provide polycondensation reaction type reinforced thermoplastic resin in long fibres, this method is applicable to various polycondensation reaction systems, and the resin that utilizes this method to make can be used for preparing the long fiber reinforced thermoplastic composites of rigidity height, good toughness.
For realizing purpose of the present invention, the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres, adopt following steps to carry out:
The preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres may further comprise the steps:
1. reaction raw materials is through esterification or transesterification reaction, and formation can be carried out the carboxylate of condensation reaction, and the change reaction conditions makes carboxylate generation melt polycondensation reaction, generates the low viscosity polycondensate, under molten state the low viscosity polycondensate is imported steeping vat;
2. with the fibre bundle pre-heating temperature elevation, under external force traction, the fibre bundle after the intensification passes the melt inside of low viscosity polycondensate in the steeping vat, and melt is attached to fiber surface and forms prepreg;
3. with prepreg cooling, pelletizing, obtain the low viscosity section;
4. the solid state polycondensation process is passed through in the low viscosity section again, generates polycondensation reaction type reinforced thermoplastic resin in long fibres.
Further, among the preparation method of above-mentioned polycondensation reaction type reinforced thermoplastic resin in long fibres, the limiting viscosity of the 1. described low viscosity polycondensate of step is in 0.45～0.65 scope; Step 2. in fibre bundle be preheated and be warming up to T ± 5 ℃, wherein T is the melt temperature of low viscosity polycondensate; Through step 4. the limiting viscosity of the resin for preparing of solid state polycondensation be 0.70～1.20.
Again further, among the preparation method of above-mentioned polycondensation reaction type reinforced thermoplastic resin in long fibres, the 1. described carboxylate of step be " polyethylene terephthalate " (PET), " Poly(Trimethylene Terephthalate) " (PTT), " polybutylene terephthalate " (PBT) or " PEN " polycondensation monomer or oligopolymer (PEN).
Further, among the above-mentioned polycondensation reaction type reinforced thermoplastic resin in long fibres preparation method, the 1. described carboxylate of step is " polyethylene terephthalate " polycondensation monomer or oligopolymer (PET), the limiting viscosity of oligopolymer melt is 0.45～0.55, temperature after the fibre bundle preheating is 265 ℃～275 ℃, and the limiting viscosity of resin is 0.70～1.20 behind the solid state polycondensation.
In addition, among the above-mentioned polycondensation reaction type reinforced thermoplastic resin in long fibres preparation method, described fibre bundle can be glass fibre, carbon fiber, flax, cellulosic fibre, chemical synthetic fiber or steel fiber; And this fibre bundle can carry out surface treatment and becomes the functionalization macrofiber through coupling agent, and then preheating, dipping.The preferred γ-An Jibingjisanyiyangjiguiwan of used coupling agent, γ-glycidyl ether propyl trimethoxy siloxanes, γ-(methacryloxy) propyl trimethoxy silicane, or vinyltrimethoxy silane.
Substantive distinguishing features and obvious improvement that the present invention gives prominence to are mainly reflected in:
(1) owing to adopt low viscous polycondensation reaction type polymkeric substance that fiber is flooded, infiltration degree height, infiltration speed are fast, and produce and carry out easily, thus the guardian technique difficult point in fundamentally having solved LFRTP work in-process production process;
(2) polymerization and dipping operation are united two into one, compare with the production technique of existing LFRTP, reduced operations such as chip drying, screw rod melt extrude, saved production cost, the oligopolymer melt viscosity that is used to flood fortifying fibre also can regulate and control;
(3) solid phase polycondensation process can carry out in vacuum drum or continous way solid phase polycondensation tower, by adjusting the temperature and time of solid phase polycondensation, can regulate the molecular weight of resin comparatively easily, and then obtain the matrix material of different molecular weight, different mechanical properties, various flows dynamic characteristic;
(4) two portions can utilize existing polycondensation reaction type full scale plant and solid phase polycondensation full scale plant to implement respectively before and after this technical scheme, both all have the production technology and the equipment of comparative maturity, make the present invention have very strong popularizing value, be easy to industrializing implementation;
(5) owing to adopt low-molecular-weight polymer impregnated fortifying fibre, oligopolymer has more end group than high molecular weight polymers, they in solid phase polycondensation and back road molding process with the surface functional group generation chemical reaction of fortifying fibre, form surface grafting, improve the interfacial adhesion of matrix material, strengthened performance of composites.
Description of drawings
Fig. 1 is a preparation method's of the present invention process flow diagram;
Fig. 2 is the course of processing synoptic diagram of PET prepreg.
Embodiment
The traditional method of preparation fiber reinforced thermoplastic resin (LFRTP resin) is to be raw material with polymkeric substance such as high-molecular weight PET, adopts twin screw extruder to melt extrude and obtains polymer melt, carries out fiber impregnation again.The present invention adopts esterification (transesterify), polycondensation, dipping, cooling, granulating integrated technology, with low-molecular-weight polycondensate impregnation of fibers bundle, through overcooling, pelletizing, obtains the prepreg section, carries out solid phase polycondensation then and obtains high molecular LFRTP resin.
As shown in Figure 1, at first with reaction raw materials process esterification or transesterification reaction, formation can be carried out the condensation system of condensation reaction in the present invention; Change reaction conditions then, make condensation system generation melt polycondensation reaction, generate the low viscosity polycondensate, and under molten state, the low viscosity polycondensate is imported steeping vat.On the other hand, through primary heater unit, make its temperature identical or close, under external force traction on successive macrofiber tow with the temperature of oligopolymer melt, fibre bundle after the intensification passes the melt inside of low viscosity polycondensate in the steeping vat, and melt is attached to fiber surface and forms prepreg.The temperature of steeping vat can be regulated, guarantee that melt has the good flow performance and don't the temperature range that can degrade in, melt fully floods fiber.The resin streak that contains fiber behind the dipping is pulled out from the die head of steeping vat, again through overcooling, granulation, obtains low viscous prepreg section.The solid state polycondensation process is passed through in this section again, just generates polycondensation reaction type LFRTP resin.
The present invention can be raw materials for production with terephthalic acid, dimethyl terephthalate (DMT), naphthalic acid, naphthalene diformic acid dimethyl ester, ethylene glycol, propylene glycol, butyleneglycol and as third and fourth monomer of modification, by esterification (or transesterify) and polycondensation, PET, PTT, the polycondensation reaction type LFRTP resins such as PBT, PEN of preparation limiting viscosity about 0.6.The polymkeric substance that makes can be a homopolymer, also can be multipolymer.Being used for the enhanced fibre bundle can be glass fibre, carbon fiber, flax, cellulosic fibre, also can be chemical synthetic fiber, or even steel fiber such as Stainless Steel Fibre, copper fiber.
Used continuous fibre can also carry out surface treatment to it with coupling agent, makes matrix material have better interfacial bond property.These coupling agents mainly are γ-An Jibingjisanyiyangjiguiwans, γ-glycidyl ether propyl trimethoxy siloxanes, γ-(methacryloxy) propyl trimethoxy silicane, vinyltrimethoxy silane or the like.
The LFRTP resin for preparing is used for road, back forming process and mainly contains dual mode, and the one, compression molding, the 2nd, injection moulding, thus make the LFRTP composite product.In the preparation process of resin, can in the low viscosity polymer melt, add suitable oxidation inhibitor, fire retardant, crystallization nucleating agent, crystallization promoter or mineral filler, the antioxygen property of raising resin, flame retardant properties, crystal property etc. satisfy the service requirements of composite product.And, by aperture that changes the immersion system die head or the macrofiber that uses different fiber numbers, can control the content of fortifying fibre in the resin; Also can add the common section that viscosity is close, do not contain fortifying fibre by a certain percentage in solid phase polycondensation or moulding process, two kinds of material mix use, to regulate the reinforced fiber content in the end article, satisfy the service requirements of different user.
Be example with preparation macrofiber REINFORCED PET resin and matrix material thereof below, technical solution of the present invention is described further.These examples only are some exemplary applications, can not be interpreted as a kind of restriction to claim protection domain of the present invention.
(1) equipment of preimpregnated material manufacture
As shown in Figure 2, reaction raw materials such as PTA, EG, catalyzer are added reactor 1, vacuumize and carry out N
2Heating up and carry out esterification in displacement back, changes polycondensation phase over to after esterification is finished, and vacuumizes, the conditioned reaction temperature makes the generation condensation reaction.When carrying out polyreaction, primary heater unit 4 and steeping vat 5 are warming up to about 260 ℃, keep temperature-stable.After oligomer viscosities reaches preset value, open the valve of reactor 1 bottom, control PET melt enters steeping vat 5 with certain flow; Simultaneously, the macrofiber tow on the creel 1 passes primary heater unit 4, steeping vat 5 and spray cooling tank 6 successively under the effect of silk guide frame 2 and tractor 7.Adjust the fiber pulling speed, make the good intensification of its acquisition and fully flood.Like this, the PET melt in the steeping vat 5 just can be attached to fiber surface well, forms the strip prepreg through spray cooling tank 6 cooling backs.This strip prepreg is extracted out from the deflector roll of tractor 7, through just obtaining low viscous prepreg section after dicing machine 8 pelletizings.
(2) solid phase polycondensation
Solid phase polycondensation carries out in the vacuum-drying rotary drum.Adopt logical N
2Method quicken the micromolecular diffusion that polycondensation produces, high-purity N
2After the pre-heating system heating, enter in the rotary drum; Rotary drum is heated by heating jacket, and the automatic temperature control system temperature control is arranged, and makes the interior temperature fluctuation of rotary drum less than 4 ℃.Rotary drum is driven by a variable speed motor, and rotating speed is adjustable.To put into rotary drum behind the above-mentioned prepreg chip drying, feed N
2Make air discharge in the rotary drum, pre-crystallization is 1 hour in the time of 120 ℃.Control nitrogen flow then, be warming up to 240 ℃ gradually and carry out solid state polycondensation, make macrofiber REINFORCED PET resin.
Particularly, limiting viscosity is that 0.45 PET prepolymer sized glass fibres carries out solid phase polycondensation again, and resin viscosity that makes and the corresponding relation of solid state polycondensation time see Table 1.
(table 1)
| Reaction times (hr) | 0 | 3 | 6 | 9 | 12 | 15 | 20 | 30 |
| Limiting viscosity | 0.450 | 0.476 | 0.605 | 0.659 | 0.678 | 0.760 | 0.807 | 0.880 |
(3) performance test
One through the macrofiber REINFORCED PET resin that 30 hours solid state polycondensations prepare, is made standard testing batten through injection moulding with above-mentioned specific examples, and its physical and chemical performance sees Table 2.
(table 2)
| Test event | Unit | Performance | Testing standard ASTM |
| Content of glass fiber | ％ | 38 | - |
| Tensile strength | MP | 181 | D638 |
| Elongation at break | ％ | 2 | D638 |
| Flexural strength | MP | 255 | D790 |
| Bending elastic modulus | MP | 9534 | D790 |
Its two, the macrofiber REINFORCED PET resin with above-mentioned specific examples prepares through 30 hours solid state polycondensations mixes by different ratios with the pure PET section of identical viscosities, the standard testing batten is made in injection moulding then, its physical and chemical performance sees Table 3.
(table 3)
| Performance | Unit | Macrofiber REINFORCED PET resin usage quantity (Wt%) | Testing method ASTM | |||
| 20 | 30 | 40 | 50 | |||
| Tensile strength | MPa | 129 | 145 | 170 | 187 | D638 |
| Elongation at break | ％ | 2 | 2 | 2 | 2 | D638 |
| Flexural strength | MPa | 172 | 207 | 244 | 292 | D790 |
| Bending elastic modulus | MPa | 5335 | 6612 | 9472 | 12858 | D790 |
| Shock strength (outstanding breach) | J/m | 169 | 171 | 252 | 231 | D256 |
| Dimension card heat-resisting (5/50) | ℃ | 246 | 246 | 246 | 238 | D1525 |
| Heat-drawn wire (1.82MPa) | ℃ | 227 | 234 | 233 | 245 | D648 |
They are three years old, above-mentioned specific examples is passed through the macrofiber REINFORCED PET resin that the different time solid state polycondensation prepares, weigh after the thorough drying, the shop places in the mould, slowly is warming up to 200 ℃ and the 2MPa that pressurizes, be incubated half an hour, be warmed up to 260 ℃ and the 5MPa that pressurizes then, the insulation half an hour after, naturally cool to room temperature, the demoulding becomes sheet material, and its mechanical property is as shown in table 4.
(table 4)
| The solid phase polycondensation time (hr) | 10 | 15 | 20 | 30 |
| Shock strength (KJ/M 2) | 102.4 | 143 | 181.6 | 221.7 |
| Flexural strength (MPa) | 480.4 | 481.5 | 510.52 | 610.6 |
| Shearing resistance (MPa) | 21.25 | 26.21 | 28.68 | 33.16 |
The testing method of three kinds of mechanical properties is respectively in the table 4:
Shock strength---according to ASTM D256-02 standard testing, shock strength P=E/H, wherein E is that impact energy, H are batten thickness;
Flexural strength---, on the multifunction electronic experimental machine, test chuck speed 0.1mm/min, flexural strength σ according to ASTM D790-02 standard
f=3PL/2/B/H
2, wherein P is that load, L are that span, B are that width, H are thickness;
Shearing resistance---according to ASTM D2344 standard, on the multifunction electronic experimental machine, test with short strutbeam three-point bending experiment, chuck speed 1mm/min, interlaminar shear strength F=0.75*P/B/H, wherein P is that load, B are that batten width, H are thickness.
Claims (9)
1. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres may further comprise the steps:
1. reaction raw materials is through esterification or transesterification reaction, and formation can be carried out the carboxylate of condensation reaction, and the change reaction conditions makes carboxylate generation melt polycondensation reaction, generates the low viscosity polycondensate, under molten state the low viscosity polycondensate is imported steeping vat;
2. with the fibre bundle pre-heating temperature elevation, under external force traction, the fibre bundle after the intensification passes the melt inside of low viscosity polycondensate in the steeping vat, and melt is attached to fiber surface and forms prepreg;
3. with prepreg cooling, pelletizing, obtain the low viscosity section;
4. the solid state polycondensation process is passed through in the low viscosity section again, generates polycondensation reaction type reinforced thermoplastic resin in long fibres.
2. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres according to claim 1, it is characterized in that: the limiting viscosity of the 1. described low viscosity polycondensate of step is in 0.45～0.65 scope.
3. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres according to claim 1 is characterized in that: step 2. in fibre bundle be preheated and be warming up to T ± 5 ℃, wherein T is the melt temperature of low viscosity polycondensate.
4. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres according to claim 1 is characterized in that: through step 4. the limiting viscosity of the resin for preparing of solid state polycondensation be 0.70～1.20.
5. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres according to claim 1, it is characterized in that: the 1. described carboxylate of step is the polycondensation monomer or the oligopolymer of " polyethylene terephthalate ", " Poly(Trimethylene Terephthalate) ", " polybutylene terephthalate " or " PEN ".
6. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres according to claim 5, it is characterized in that: polycondensation monomer or oligopolymer that the 1. described carboxylate of step is " polyethylene terephthalate ", the limiting viscosity of oligopolymer melt is 0.45～0.55, temperature after the fibre bundle preheating is 265 ℃～275 ℃, and the limiting viscosity of resin is 0.70～1.20 behind the solid state polycondensation.
7. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres according to claim 1, it is characterized in that: described fibre bundle is glass fibre, carbon fiber, flax, cellulosic fibre, chemical synthetic fiber or steel fiber.
8. according to the preparation method of claim 1 or 7 described polycondensation reaction type reinforced thermoplastic resin in long fibres, it is characterized in that: described fibre bundle carries out surface treatment through coupling agent and becomes the functionalization macrofiber, and then preheating, dipping.
9. the preparation method of polycondensation reaction type reinforced thermoplastic resin in long fibres according to claim 8, it is characterized in that: described coupling agent is γ-An Jibingjisanyiyangjiguiwan, γ-glycidyl ether propyl trimethoxy siloxanes, γ-(methacryloxy) propyl trimethoxy silicane, or vinyltrimethoxy silane.
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| CN102107536A (en) * | 2010-12-22 | 2011-06-29 | 金发科技股份有限公司 | Forming equipment and forming method for macrofiber-reinforced thermoplastic resin |
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| CN103272530A (en) * | 2013-06-01 | 2013-09-04 | 张家港市宝田新型材料科技有限公司 | Feeding device for esterification reactor |
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| EP0340818A1 (en) * | 1988-04-05 | 1989-11-08 | Dsm N.V. | Polyamide moulded article and a process for the production thereof |
| US5433419A (en) * | 1991-11-28 | 1995-07-18 | Polyplastics Co., Ltd. | Method for forming fiber-reinforced molding pellets |
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| CN100418740C (en) * | 2001-12-30 | 2008-09-17 | 上海杰事杰新材料股份有限公司 | Manufacturing method of continuous long fiber reinforced reaction type resin |
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Effective date of registration: 20160206 Address after: 211900 Yizheng Changjiang Road, Jiangsu, China, No. 1, No. Patentee after: CHINA SINOPEC YIZHENG CHEMICAL FIBER CO., LTD. Address before: 211900 No. 1 West Changjiang Road, Xu Town, Jiangsu City, Yizheng Province Patentee before: Yizheng Chemical Fiber Co., Ltd., China Petrochemical Group Corp. |