CN108943773A - The preparation method of pultrusion polyurethane fiber enhancing composite material - Google Patents
The preparation method of pultrusion polyurethane fiber enhancing composite material Download PDFInfo
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- CN108943773A CN108943773A CN201810592882.3A CN201810592882A CN108943773A CN 108943773 A CN108943773 A CN 108943773A CN 201810592882 A CN201810592882 A CN 201810592882A CN 108943773 A CN108943773 A CN 108943773A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/523—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement in the die
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/525—Component parts, details or accessories; Auxiliary operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The invention discloses a kind of preparation methods of pultrusion polyurethane fiber enhancing composite material, comprise the steps of: that the head for the continuous fiber for being 50-85% by mass fraction passes through mold, the mold at least has injecting glue soak band, pre-forming area and curing area；Being impregnated with the continuous fiber being located in injecting glue soak band completely by the polyurethane resin of high pressure；The head of continuous fiber is moved under the draw of traction device, is moved to the continuous fiber being impregnated with by polyurethane resin in pre-forming area in draw and is carried out heated gel, obtains preforming continuous fiber reinforced composite materials；With the continuous traction active force that traction device generates, preforming continuous fiber reinforced composite materials is made to pulled into mold exterior after the curing molding of curing area.Preparation method of the invention can avoid blocking mold after improving continuous fiber content.
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of pultrusion polyurethane fiber enhancing composite material
Preparation method.
Background technique
Glass fibre reinforced composion is mainly one kind using glass fibre and unsaturated polyester (UP) as matrix currently on the market
The composite material of material.As one kind of composite material, glass fibre reinforced composion is navigating because of its unique performance advantage
It has been obtained in empty space flight, railway, decorative architecture, family's living furniture, building materials bathroom and sanitation project etc. relevant industries extensively
Using.
Existing a part of glass fibre reinforced composion is made using pultrude process, specifically: in traction device
Under traction, glass fibre is by resin storage tank by first preforming in a mold and heated after unsaturated polyester progress thorough impregnation
It is allowed to curing molding, glass fiber reinforced plastic shapes are made, is finally cut into the glass fiber reinforced plastics product of required length.For example, continuous fiber reinforcement
The preparation method of continuous fibre enhancement polyurethane composite material is disclosed in the article of the mechanical property of compound polyurethane material, is had
Body is as follows:
Adhesive is made by scientific matching in the white material for synthesizing PUR (enhancing polyurethane) resin and black material, is added to and pours
It infuses in box.It is enhancing material with continuous GF (continuous fiber), composite felt and surface felt, immersing in casting box is sufficiently impregnated it, passes through
GF is gradually become profile identical with Oral incision by pre-shaping device, while squeezing out extra PUR, then passes through pultrusion mouth mold
Composite molding is carried out using pultrude process, thirdly the temperature of area preheating zone, gel area and curing area is respectively between 180~210 DEG C
It adjusts, cured PUR/GF composite material is pulled out from mold with the hauling speed of 15~20cm/min.Most afterwards through air-cooled
Solidify and obtains the thermosetting property PUR/GF high-performance composite materials that GF mass fraction is up to 70.5%.
Although the mass fraction of GF made from above-mentioned technique reaches 70.5%, there is also following defects for above-mentioned technique:
(1) different from unsaturated polyester when GF, composite felt and surface felt are immersed in casting box in above-mentioned technique
Place is that the setting rate of unsaturated polyester is slow, and the setting rate of polyurethane is fast, will lead to polyurethane and is not in time for also pair
GF, composite felt and surface felt are impregnated with completely, and polyurethane has just solidified, thus the GF for having polyurethane is input to mould
When in tool, there is GF and the case where blocking is formed to mold.
(2) GF is gradually become profile identical with Oral incision by the preformed device recorded in above-mentioned technique, simultaneously
Squeeze out extra PUR, it is thus evident that since polyurethane can not be impregnated with GF completely, result in surface and the internal residual of GF it is extra
Polyurethane, these extra PUR are extruded, and also showing above-mentioned technique, there is the wastes of polyurethane.
(3) the pull-out speed of above-mentioned cured PUR/GF composite material is slow, causes production efficiency low.
(4) in material made from the above method, the mass fraction of GF is up to 70.5%, if however, this method after
The continuous content for increasing glass fibre, it is thus evident that blocked the result is that certainly will be formed to mold.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of pultrusion polyurethane fiber enhancing composite material, this hairs
Bright preparation method can avoid blocking mold after improving fiber content.
The technical solution for solving above-mentioned technical problem is as follows:
The preparation method of pultrusion polyurethane fiber enhancing composite material comprising the steps of:
Head by mass fraction for 50-85% continuous fiber passes through mold, and the mold is at least impregnated with injecting glue
Area, pre-forming area and curing area；
The polyurethane resin of synthesizing in situ is injected into mold in a manner of high pressure polyurethane resin injection system
In injecting glue soak band, it is impregnated with the continuous fiber being located in injecting glue soak band completely by the polyurethane resin of high pressure；
The head of continuous fiber is moved under the draw of traction device, makes the continuous fiber being impregnated with by polyurethane resin
It is moved in pre-forming area in draw and carries out heated gel, obtain preforming continuous fiber reinforced composite materials；
With the continuous traction active force that traction device generates, make preforming continuous fiber reinforced composite materials by solid
Mold exterior is pulled into after changing area's curing molding.
The present invention has the advantages that by adding injecting glue soak band on mold, and by the way of injecting glue in mould, this
Sample, by polyurethane resin injection system by synthesizing in situ polyurethane resin, the advantage that: it 1. realizes real to polyurethane viscosity
When control, it is convenient that production line is opened to guarantee that fiber well impregnates the real-time control 2. realized to polyurethane gelling time
Stop control 3. to realize to the rapid real-time control of polyurethane polymerization, to improve shaping speed, is based on upper injecting glue mode and mold, it is poly-
, can be with real-time control dip time when urethane resin and continuous fiber (or glass fibre and glass mat) are impregnated, this
Sample can avoid not yet being impregnated with glass (or glass fibre and glass mat) i.e. preforming solidification afterwards by polyurethane resin, thus
It avoids the continuous fiber after being not yet impregnated with by polyurethane resin (or glass fibre and glass mat) and enters pre-forming area
When blocking.In addition, the polyurethane resin with pressure is injected into mold, polyurethane resin is under the action of certain pressure
With better mobility, therefore, the polyurethane resin acceleration of these flowings is impregnated with continuous fiber, further increases extruding equipment
Pultrusion speed, meanwhile, also avoid with polyurethane resin poor fluidity of the continuous fiber after compound and by polyurethane resin still
Continuous fiber (or glass fibre and fibrofelt) after not being impregnated with enters blocking when pre-forming area.Therefore, system of the invention
Preparation Method still will not block up mould when the content for making continuous fiber is up to 85%, and increase continuous fiber content and had
Remarkable result be so that the performance of product is promoted (intensity, bending property etc.).
Specific embodiment
Embodiment one:
The preparation method of pultrusion polyurethane fiber enhancing composite material of the invention comprising the steps of:
Step 1, by be located at continuous fiber around fibrofelt and mass fraction be 50% continuous fiber head according to
Secondary to pass through track yarn guide and mold, the continuous fiber includes glass fibre, aramid fiber, basalt fibre, carbon fiber, gold
Belong to fiber and its any mixture, fibrofelt is glass mat, aramid fiber felt, basalt fibre felt, carbon fiber felt, metal
Fibrofelt etc..Track yarn guide is located at the upstream of mold, on the yarn guide of track at least provided with one passed through for continuous fiber
One through-hole, the second through-hole also passed through at least provided with one for fibrofelt on the yarn guide of track, these second through-holes are located at first
Around through-hole, wherein continuous fiber is then passed through the mold after passing through the first through hole, after fibrofelt passes through the second through-hole
It is then passed through the mold, fibrofelt and continuous fiber are synchronized to draw after passing through mold by traction device.
The mold at least has injecting glue soak band, pre-forming area and curing area；The total length of mold is 120cm,
The length of middle injecting glue soak band is 60cm, and the length of pre-forming area and curing area is 60cm.
Step 2, the polyurethane resin of synthesizing in situ is injected into a manner of high pressure polyurethane resin injection system
In the injecting glue soak band of mold, i.e., the polyurethane resin less than or equal to 7MPa is injected into mould with the speed of 50~4800ml/min
In the injecting glue soak band of tool, in the present embodiment, the pressure for the polyurethane resin being injected into the injecting glue soak band of mold is
0.2MPa, and polyurethane resin is injected into injecting glue soak band with the speed of 547ml/min.By the polyurethane resin with pressure
It is injected into the injecting glue soak band of mold, makes the continuous fiber being located in injecting glue soak band and fibrofelt by the polyurethane tree of high pressure
Rouge is impregnated with completely；Polyurethane resin injection system is the model of Beijing Jinghua Pike Polymer Mechanical Equipment Co., Ltd.'s production
The injection system of JHPK-G20A.
Angle between the axial direction and continuous fiber direction of advance of gum-injecting port on the injecting glue soak band is obtuse angle, this is blunt
Preferably for 90.5 to 135 degree, obtuse angle is 95 degree to the size at angle, is advantageous in that using obtuse angle, poly- ammonia is being injected into mold
When ester resin, flow polyurethane resin along the direction that continuous fiber moves, so that polyurethane resin has more in mold
Good mobility, is conducive to that polyurethane resin is made to play help to being impregnated with completely for continuous fiber in this way.
Step 3, the head of continuous fiber and fibrofelt is moved under the draw of traction device, is made by polyurethane resin
The continuous fiber being impregnated with is moved in pre-forming area in draw to be heated, and it is multiple to obtain preforming continuous fiber reinforcement
Condensation material；
Pre-forming area is by preheating zone and gel district's groups at wherein the heating temperature of preheating zone is 50-140 DEG C, gel area
Heating temperature is 150-200 DEG C, it is preferable that the heating temperature of preheating zone is 120 DEG C, and the heating temperature in gel area is 170 DEG C.
Step 4, with the continuous traction active force that traction device generates, make preforming continuous fiber reinforced composite materials
Mold exterior is pulled into after the curing molding of curing area.The hauling speed of the traction device is 15~1830cm/min,
Preferably, the hauling speed of the traction device is 1750cm/min.
Embodiment two:
The present embodiment and one difference of embodiment are as follows:
It is the head that will be located at the continuous fiber that the fibrofelt around continuous fiber and mass fraction are 60% in step 1
Portion sequentially passes through track yarn guide and mold；
In step 2, the pressure for being injected into the polyurethane resin in the injecting glue soak band of mold is 0.15MPa, and with
The speed of 563ml/min injects polyurethane resin into injecting glue soak band.
In step 3, the heating temperature of preheating zone is 100 DEG C, and the heating temperature in gel area is 180 DEG C.
In step 4, the hauling speed of the traction device is 1500cm/min.
Embodiment three:
The present embodiment and one difference of embodiment are as follows:
It is the head that will be located at the continuous fiber that the fibrofelt around continuous fiber and mass fraction are 70% in step 1
Portion sequentially passes through track yarn guide and mold.
In step 2, the pressure for being injected into the polyurethane resin in the injecting glue soak band of mold is 0.17MPa, and with
The speed of 233ml/min injects polyurethane resin into injecting glue soak band.
In step 3, the heating temperature of preheating zone is 90 DEG C, and the heating temperature in gel area is 175 DEG C.
In step 4, the hauling speed of the traction device is 1240cm/min.
Example IV:
The present embodiment and one difference of embodiment are as follows:
It is the head that will be located at the continuous fiber that the fibrofelt around continuous fiber and mass fraction are 75% in step 1
Portion sequentially passes through track yarn guide and mold.；
In step 2, the pressure for being injected into the polyurethane resin in the injecting glue soak band of mold is 0.18MPa, and with
The speed of 141ml/min injects polyurethane resin into injecting glue soak band.
In step 3, the heating temperature of preheating zone is 80 DEG C, and the heating temperature in gel area is 160 DEG C.
In step 4, the hauling speed of the traction device is 90cm/min.
Embodiment five:
The present embodiment and one difference of embodiment are as follows:
It is the head that will be located at the continuous fiber that the fibrofelt around continuous fiber and mass fraction are 80% in step 1
Portion sequentially passes through track yarn guide and mold.
In step 2, the pressure for being injected into the polyurethane resin in the injecting glue soak band of mold is 0.2MPa, and with 75ml/
The speed of min injects polyurethane resin into injecting glue soak band.
In step 3, the heating temperature of preheating zone is 60 DEG C, and the heating temperature in gel area is 190 DEG C.
In step 4, the hauling speed of the traction device is 60cm/min.
Embodiment six:
The present embodiment and one difference of embodiment are as follows:
It is the head that will be located at the continuous fiber that the fibrofelt around continuous fiber and mass fraction are 81% in step 1
Portion sequentially passes through track yarn guide and mold.
In step 2, the pressure for being injected into the polyurethane resin in the injecting glue soak band of mold is 0.2MPa, and with 60ml/
The speed of min injects polyurethane resin into injecting glue soak band.
In step 3, the heating temperature of preheating zone is 70 DEG C, and the heating temperature in gel area is 180 DEG C.
In step 4, the hauling speed of the traction device is 50cm/min.
Embodiment seven:
The present embodiment and one difference of embodiment are as follows:
It is that will be located at the continuous fiber that the fibrofelt around continuous fiber and mass fraction are 80.5% in step 1
Head sequentially passes through track yarn guide and mold.
In step 2, the pressure for being injected into the polyurethane resin in the injecting glue soak band of mold is 0.2MPa, and with 61ml/
The speed of min injects polyurethane resin into injecting glue soak band.
In step 3, the heating temperature of preheating zone is 65 DEG C, and the heating temperature in gel area is 175 DEG C.
In step 4, the hauling speed of the traction device is 50cm/min.
Embodiment eight:
The present embodiment and one difference of embodiment are as follows:
It is the head that will be located at the continuous fiber that the fibrofelt around continuous fiber and mass fraction are 79% in step 1
Portion sequentially passes through track yarn guide and mold.
In step 2, the pressure for being injected into the polyurethane resin in the injecting glue soak band of mold is 0.2MPa, and with 72ml/
The speed of min injects polyurethane resin into injecting glue soak band.
In step 3, the heating temperature of preheating zone is 80 DEG C, and the heating temperature in gel area is 165 DEG C.
In step 4, the hauling speed of the traction device is 55cm/min.
4 continuous fiber composite materials made of embodiment five to embodiment eight are cut into 1.5 meters of long samples by applicant
(sample specification model are as follows: 28 × 56 profile of double C-type), is sent to continuous fiber studying and designing institute, Nanjing Product Quality Verification Centers, and country is continuous
Fiber product Quality Supervision and Inspection Center tests, the requirement of inspection are as follows: carries out tensile strength to Samples Submitted, stretches bullet
Property modulus, maximum stress in bend, bending stress, bending elastic modulus, short beam interlaminar shear strength, compression are strong at 1.5 times of thickness
Degree is tested, and the survey report that above-mentioned unit is provided is as follows:
It is numbered in the inspection of above-mentioned unit are as follows: glass quality inspection (QSW) word (18040115) number
Preparation method according to the present invention and check conclusion can be seen that the present invention and have a characteristic that
1. pultrusion speed is improved, to improve the production efficiency of production line；
2. as glass fiber content increases, amount of resin is reduced, and (price of resin is being greatly lowered for the totle drilling cost of profile
5 to 10 times of glass price)；
3. quickly injection may be implemented and be impregnated with uniformly under certain linear velocity；
4. the tensile strength and bending strength of profile are improved with the increase of glass fiber content；
5. appointing so can be high due to realizing that glass fiber content is more than 80% mass fraction using high-pressure injection plastic and track yarn guide
Fast pultrusion and do not block mold.
Claims (10)
1. the preparation method of pultrusion polyurethane fiber enhancing composite material, which is characterized in that comprise the steps of:
By mass fraction be 50-85% continuous fiber head pass through mold, the mold at least have injecting glue soak band,
Pre-forming area and curing area；
The polyurethane resin of synthesizing in situ is injected into the injecting glue of mold polyurethane resin injection system in a manner of high pressure
In soak band, it is impregnated with the continuous fiber being located in injecting glue soak band completely by the polyurethane resin of high pressure；
The head of continuous fiber is moved under the draw of traction device, is leading the continuous fiber being impregnated with by polyurethane resin
The effect of drawing is moved to progress heated gel in pre-forming area, obtains preforming continuous fiber reinforced composite materials；
With the continuous traction active force that traction device generates, make preforming continuous fiber reinforced composite materials by curing area
Mold exterior is pulled into after curing molding.
2. the preparation method of pultrusion polyurethane fiber enhancing composite material according to claim 1, which is characterized in that
It further include the fibrofelt for being synchronized traction by traction device with continuous fiber after mold, fibrofelt is located at continuous fiber week
It encloses.
3. the preparation method of pultrusion polyurethane fiber enhancing composite material according to claim 2, which is characterized in that
It further include track yarn guide, which is located at the upstream of mold, supplies on the yarn guide of track at least provided with one continuous fine
Tie up across first through hole, be additionally provided at least one second through-hole passed through for fibrofelt on the yarn guide of track, these are second logical
Hole is located at around first through hole, and the continuous fiber is then passed through the mold, the fibrofelt after passing through the first through hole
The mold is then passed through after the second through-hole.
4. special according to claim 1 to the preparation method of the enhancing composite material of pultrusion polyurethane fiber described in one of 3
Sign is that the total length of mold is 90~150cm, and wherein the length of injecting glue soak band is 30~70cm.
5. special according to claim 1 to the preparation method of the enhancing composite material of pultrusion polyurethane fiber described in one of 3
Sign is that the angle between the axial direction and continuous fiber direction of advance of the gum-injecting port on the injecting glue soak band is obtuse angle.
6. special according to claim 1 to the preparation method of the enhancing composite material of pultrusion polyurethane fiber described in one of 3
Sign is, injects polyurethane resin into injecting glue soak band with the speed of 50~4800ml/min.
7. special according to claim 1 to the preparation method of the enhancing composite material of pultrusion polyurethane fiber described in one of 3
Sign is that the pressure of the polyurethane resin being injected into mold is less than or equal to 7MPa.
8. the preparation method of pultrusion polyurethane fiber enhancing composite material according to claim 7, which is characterized in that
The pressure of the polyurethane resin being injected into mold is 0.2MPa.
9. special according to claim 1 to the preparation method of the enhancing composite material of pultrusion polyurethane fiber described in one of 3
Sign is that the hauling speed of the traction device is 15~1830cm/min.
10. enhance the preparation method of composite material to pultrusion polyurethane fiber described in one of 3 according to claim 1,
It is characterized in that, the mass fraction of continuous fiber is 65~80%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109483916A (en) * | 2019-01-09 | 2019-03-19 | 浙江新纳复合材料有限公司 | A kind of preparation of polyurethane-type composite material bar material |
| CN109483913A (en) * | 2019-01-09 | 2019-03-19 | 浙江新纳复合材料有限公司 | A kind of low temperature fast pultrusion moulding process of composite material |
| CN109551788A (en) * | 2019-01-14 | 2019-04-02 | 南通中格新材料科技有限公司 | A kind of polyurethane resin composite material processing method and monoblock type injection molding |
| CN109572001A (en) * | 2018-12-27 | 2019-04-05 | 上海克络蒂材料科技发展有限公司 | A kind of production technology of fiber reinforcement polyurethane composite material |
| CN110202804A (en) * | 2019-05-29 | 2019-09-06 | 南京聚发新材料有限公司 | A kind of building polyurethane resin composite material and its pultrusion molding process |
| CN111171555A (en) * | 2020-03-10 | 2020-05-19 | 云南孚道体育设施科技有限公司 | Modified polyurethane resin composite material for artificial grass filaments and preparation method thereof |
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| CN113400685A (en) * | 2021-06-11 | 2021-09-17 | 山东明珠材料科技有限公司 | Preparation method of pultrusion type polyurethane fiber reinforced composite material |
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| CN109572001A (en) * | 2018-12-27 | 2019-04-05 | 上海克络蒂材料科技发展有限公司 | A kind of production technology of fiber reinforcement polyurethane composite material |
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| CN109483916A (en) * | 2019-01-09 | 2019-03-19 | 浙江新纳复合材料有限公司 | A kind of preparation of polyurethane-type composite material bar material |
| CN109551788B (en) * | 2019-01-14 | 2023-09-08 | 南通中格新材料科技有限公司 | Polyurethane resin composite profile processing method |
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| CN111748073B (en) * | 2019-03-26 | 2024-06-11 | 科思创德国股份有限公司 | Method for preparing polyurethane pultrusion composite material |
| CN110202804A (en) * | 2019-05-29 | 2019-09-06 | 南京聚发新材料有限公司 | A kind of building polyurethane resin composite material and its pultrusion molding process |
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| CN113400685A (en) * | 2021-06-11 | 2021-09-17 | 山东明珠材料科技有限公司 | Preparation method of pultrusion type polyurethane fiber reinforced composite material |
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Application publication date: 20181207 |