CN110172134A - A kind of hydrolysis resistant polyurethane pultrusion resin composite materials and preparation method thereof - Google Patents
A kind of hydrolysis resistant polyurethane pultrusion resin composite materials and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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Abstract
The invention discloses a kind of hydrolysis resistant polyurethane pultrusion resin composite materials and preparation method thereof, belong to dual-component polyurethane resin art.Preparation including step S1, B component hydrolysis Type Polyurethane Prepolymer；Step S2, the preparation of component A polyol crosslink agent；Step S3, two components in step S1 and step S2 are transferred to bi-component in two storage tanks of colloid system respectively；Step S4, the continuous fiber for being soaked with resin is passed through into die material curing molding by dual-component polyurethane pultrusion system.The polyurethane glass fiber reinforced plastics composite material that the present invention is prepared through the above steps can have the characteristics that mechanical strength is high, hydrolytic resistance is good simultaneously.
Description
Technical field
The invention belongs to dual-component polyurethane resin art, especially a kind of hydrolysis resistant polyurethane pultrusion resin compounded
Material and preparation method thereof.
Background technique
The simple overview of pultrude process is when being soaked with the fiber of resin to pass through die material, and resin is solid under the pulling force of dragger
Change and formed by extrusion and tension, have many advantages, such as simple process it is efficient, can continuous production, product fiber content it is high.Traditional pultrude process is more
Using unsaturated-resin, vinylite and epoxy resin etc., unsaturated-resin and vinylite contain big weight phenylethylene, right
Human and environment is harmful, and its curing agent is mostly peroxide, inflammable and explosive to be not easy to store；Epoxy resin cure is slow, production efficiency
It is extremely low, and in most cases, product is firmly crisp, and toughness is insufficient.
Polyurethane resin has that curing rate is fast, high production efficiency, properties of product are strong, more friendly etc. many with human and environment
Advantage, the application on pultrude process gradually increases in recent years.Existing pultrude process mostly uses more phenyl first with polyurethane resin
Alkane polyisocyanates (polymeric MDI) is B component, polyether polyol mixtures are component A to prepare resin and be used for compound
The preparation of material.As the prior art one discloses a kind of drawing using polymeric MDI as B component, polyether polyol mixtures for component A
The preparation method of extruding process dual-component polyurethane resin；It is poly- that the prior art two discloses a kind of two-component with flame retarding function
The preparation method of urethane resin, it is B component, polyether polyol mixtures for component A that matrix resin, which is still using polymeric MDI,
Fire retardant is added on the basis of this matrix resin to be prepared.
The water resistance of polyesther resins is preferable, but mechanical property is poor compared with polyester resin, some inventions are to polyurethane thus
Resin formula is modified.As the patent prior art three and the prior art four disclose the system of polyester urethane resin of preparing
Preparation Method, but the hydrolytic resistance for how improving polyester is not clearly stated；The patent prior art five discloses one kind can be with
The method for preparing double component polyester type polyurethane resin, B component are still polymeric MDI, to solve the problems, such as polyester facile hydrolysis, are taken
The method for adding expensive hydrolysis agent；The prior art six discloses a kind of side that can prepare polyester polyether mixed type resin
Method, though a certain proportion of polycarbonate glycol is added in polyether polyol mixtures can be improved resin mechanical property, not
Consider polycarbonate hydrolysis problem, while the addition of polycarbonate can improve resin overall viscosity, be unfavorable for resin with fiber
Infiltration.
Summary of the invention
Goal of the invention: to overcome the above-mentioned prior art insufficient, the present invention provides a kind of prepare and has both hydrophobicity and resistant to hydrolysis
Property B component, thus B component and the two-component with excellent mechanical performance and hydrolytic Resistance of polyester-type component A composition it is poly-
The composite material that urethane resin and thus resin are basis material, prepared by the pultrude process of continuous fiber reinforcement material.
Technical solution: a kind of preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials includes the following steps:
Step S1, the preparation of B component hydrolysis Type Polyurethane Prepolymer takes out the polyalcohol with hydrophobic function at 120 DEG C
Vacuum 2h is cooled to 80 DEG C, and excessive Carbodiimide-Modified isocyanates is added, and in reacting 2~3h at this temperature, obtains
Base polyurethane prepolymer for use as with certain NCO content；
Step S2, the preparation of component A polyol crosslink agent, each component and weight proportion are specific as follows:
55% ~ 80wt% of polyester polyol；
10% ~ 20wt% of vegetable oil polyol；
2% ~ 8wt% of release agent；
2% ~ 5wt% of deicer；
0.2 ~ 1wt% of catalyst；
0 ~ 25%wt% of filler；
0.5% ~ 1wt% of ultraviolet absorbing agent；
0.5 ~ 1wt% of anti-aging agent；
Step S3, two components in step S1 and step S2 are transferred to bi-component in 2 storage tanks of colloid system respectively；
Step S4, the continuous fiber for being soaked with resin is passed through into die material curing molding by dual-component polyurethane pultrusion system.
In a further embodiment, the polyalcohol in the step S1 with hydrophobic function is castor oil polyhydric alcohol or divides
One of the end hydroxy butadiene polyalcohol that son amount is 1000g/mol and 2000g/mol；The anti-aging agent is 2,5- bis- special
One of butylhydroquinone or thio-2 acid two (18) ester；
In a further embodiment, the NCO content of performed polymer is finally made in the step S1 15%~27%.
In a further embodiment, vegetable oil polyol is castor oil polyhydric alcohol in the step S2；The water removal
Agent is 3A activated molecular sieve, using preceding in 250 DEG C of baking 6h or more；The catalyst is delaying type catalyst；The filler is
One of calcium carbonate, aluminium hydroxide and talcum powder；The ultraviolet absorbing agent is one of benzophenone or benzotriazole.
In a further embodiment, the two-component in the step S3 includes A batch can, B batch can, AB material for colloid system
The modules such as two metering pumps being separately connected below tank and the static mixer for mixing AB material, injecting glue frequency is 0.2~
2Hz, injecting glue amount are 50~200g/ times.
In a further embodiment, the dual-component polyurethane pultrusion system in the step S4 contains creel, guide dress
It sets, the modules such as glue-injection box, segmentally heating mold and dragger；Wherein, for colloid system with glue-injection box it is closed be connected, segmentally heating mould
3rd area Ju Wei is heated, the first two area's temperature range is 150~250 DEG C, and third area temperature range is room temperature~180 DEG C, is led
Drawing machine travel rate is 10~280cm/min.
In a further embodiment, the step S4 includes following four step:
The A material and B that S401, measured pump are got according to a certain percentage expect to enter dual-component polyurethane after static mixer mixes
In the closed glue-injection box of pultrusion system；
S402, the continuous fiber drawn from creel are through feed carrier, under the drive of dragger, with some tension and certain speed
It is sufficiently mixed and is infiltrated into glue-injection box, and with above-mentioned steps S401 resin for getting to its inside；
S403, by the heating in mold leading portion and middle section, the continuous fiber through resin infiltration at the 2/3 of mold overall length or so,
Resin rapid curing at temperature and the collective effect of catalyst, is formed with the composite material of intensity.
Slight shrinkage can occur while S404, resin solidification, under the collective effect of release agent, go out in mold endpiece
Mould.
The utility model has the advantages that the present invention relates to a kind of hydrolysis resistant polyurethane pultrusion resin composite materials and preparation method thereof,
The available resin for having both mechanical property and hydrolytic Resistance of the method provided through the invention, resistant to hydrolysis principle are B group
A large amount of carbodiimide group can be crosslinked quickly with the carboxyl that polyester hydrolysis generates and react on oligomer in point, so that sending out
The polyester molecule chain of raw fracture is quickly re-linked in the cross-linked network of polymeric inner by carbodiimide, guarantees that resin is whole
Mechanical property does not decline.
Specific embodiment
In the following description, a large amount of concrete details are given so as to provide a more thorough understanding of the present invention.So
And it is obvious to the skilled person that the present invention may not need one or more of these details and be able to
Implement.In other examples, in order to avoid confusion with the present invention, for some technical characteristics well known in the art not into
Row description.
The embodiment of the present invention is described below in detail, the example of the embodiment described is intended to explain the present invention, and cannot manage
Solution is limitation of the present invention.Particular technique and reaction condition person are not specified in embodiment, it can institute according to the literature in the art
The technology or conditions or product description of description carry out.All reagents or instrument that manufacturer is not specified, can pass through commercially available acquisition.
Embodiment 1
A kind of preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials, comprising:
The preparation of B component: weighing 93 kilograms of castor oil and be added in closed reactor, be warming up to 120 DEG C, takes out while stirring true
Sky stops after 2h vacuumizing and heating, and is cooled to 80 DEG C and the Carbodiimide-Modified that 121.6 kilograms of trades mark are 100LL is added
MDI(Wan Hua company), the reaction was continued 2h obtains the performed polymer that NCO content is 27%.
The preparation of component A: 80 kilograms of polyester 2915(Si Taipan companies are weighed respectively), it is 10 kilograms of castor oil polyhydric alcohols, 8 public
Jin 550D release agent (Technick Products company), 2 kilograms of 3A activated molecular sieve, catalyst that high-temperature baking is crossed
0.5 kilogram of FOMREZ UL-28 and totally 1 kilogram of 0.5 kilogram of K-5218,1 kilogram of ultraviolet absorbing agent benzophenone and 1 kilogram are anti-
Old agent 2,5- ditert-butylhydro quinone is added in stirred tank and stirs evenly.
Component A and B component are directed respectively into bi-component in colloid system two storage tanks of corresponding A and B, glass fibre from
Creel forms certain tension through thread board under the drive of dragger, and with the speed of 280cm/min by being connected with two-component
For colloid system glue-injection box (two-component for colloid system injecting glue frequency be 2Hz, each injecting glue amount be 200g, B material with A expect weight ratio
It for 1:1), and is allowed to sufficiently infiltrate with AB component hybrid resin, into mold, (three area's temperature are respectively 150 DEG C, 180 DEG C and 160
DEG C), resin curing molding and leaves mold at high temperature.
Mechanics Performance Testing: tensile strength is carried out according to composite material of the national standard GB/T 16421-1996 to preparation, is stretched
The test of modulus, elongation at break, bending strength and bending modulus；
Hydrolytic resistance test: the batten prepared according to above-mentioned standard is placed in the hydrothermal aging case of 85 DEG C and 85% humidity
1000h takes out and tests its mechanical property and down ratio.
Embodiment 2
The preparation of B component: it weighs the end hydroxy butadiene that 100 kilogram molecular weights are 1000g/mol and is added to closed reactor
It is interior, 120 DEG C are warming up to, is vacuumized while stirring, stops vacuumizing and heating after 2h, 80 DEG C is cooled to and 54.5 kilograms of boards is added
Number Carbodiimide-Modified MDI(Hensel Mann for being 2020), the reaction was continued 2h obtains the performed polymer that NCO content is 15%.
The preparation of component A: 55 kilograms of polyester 3050(Paasche support companies are weighed respectively), it is 20 kilograms of castor oil polyhydric alcohols, 2 public
Jin 1948MCH release agent (AXEL Plastics company), 5 kilograms of 3A activated molecular sieve, catalyst that high-temperature baking is crossed
0.1 kilogram of FOMREZ UL-29 and totally 1 kilogram of 0.1 kilogram of K-5218,25 kilograms of filling aluminium hydrates, 0.5 kilogram of ultraviolet light are inhaled
It receives agent benzotriazole and 0.5 kilogram of anti-aging agent thio-2 acid two (18) ester is added in stirred tank and stirs evenly.
Component A and B component are directed respectively into bi-component in colloid system two storage tanks of corresponding A and B, glass fibre from
Creel forms certain tension through thread board under the drive of dragger, and is supplied with the speed of 10cm/min by being connected with two-component
(two-component is 0.2Hz for colloid system injecting glue frequency to the glue-injection box of colloid system, and each injecting glue amount is 50g, and B material is with A material weight ratio
1.6:1), it and is allowed to sufficiently infiltrate with AB component hybrid resin, into mold, (three area's temperature are respectively 200 DEG C, 250 DEG C and room
Temperature), resin curing molding and leaves mold at high temperature.
Mechanics Performance Testing: tensile strength is carried out according to composite material of the national standard GB/T 16421-1996 to preparation, is stretched
The test of modulus, elongation at break, bending strength and bending modulus.
Hydrolytic resistance test: the batten prepared according to above-mentioned standard is placed in the hydrothermal aging case of 85 DEG C and 85% humidity
1000h takes out and tests its mechanical property and down ratio.
Embodiment 3
The preparation of B component: it weighs the end hydroxy butadiene that 100 kilogram molecular weights are 2000g/mol and is added to closed reactor
It is interior, 120 DEG C are warming up to, is vacuumized while stirring, stops vacuumizing and heating after 2h, 80 DEG C is cooled to and 63.6 kilograms of boards is added
Number Carbodiimide-Modified MDI(BASF AG for being MM103C), the reaction was continued 2h obtains the pre-polymerization that NCO content is 20%
Body.
The preparation of component A: 70 kilograms of polyester 3050(Paasche support companies are weighed respectively), it is 15 kilograms of castor oil polyhydric alcohols, 4 public
Jin 1948MCH release agent (AXEL Plastics company), 3 kilograms of 3A activated molecular sieve, catalyst that high-temperature baking is crossed
0.4 kilogram of FOMREZ UL-29 and totally 0.7 kilogram of 0.3 kilogram of K-5218,10 kilograms of pearl fillers, 0.75 kilogram of ultraviolet light are inhaled
It receives agent benzotriazole and 0.75 kilogram of anti-aging agent thio-2 acid two (18) ester is added in stirred tank and stirs evenly.
Component A and B component are directed respectively into bi-component in colloid system two storage tanks of corresponding A and B, glass fibre from
Creel forms certain tension through thread board under the drive of dragger, and is supplied with the speed of 50cm/min by being connected with two-component
(two-component is 1Hz for colloid system injecting glue frequency to the glue-injection box of colloid system, and each injecting glue amount is 100g, and B material is with A material weight ratio
1.5:1), it and is allowed to sufficiently infiltrate with AB component hybrid resin, into mold, (three area's temperature are respectively 250 DEG C, 150 DEG C and 100
DEG C), resin curing molding and leaves mold at high temperature.
Mechanics Performance Testing: tensile strength is carried out according to composite material of the national standard GB/T 16421-1996 to preparation, is stretched
The test of modulus, elongation at break, bending strength and bending modulus；
Hydrolytic resistance test: the batten prepared according to above-mentioned standard is placed in the hydrothermal aging case of 85 DEG C and 85% humidity
1000h takes out and tests its mechanical property and down ratio.
Embodiment 4
The preparation of B component: it is polynary for the end hydroxy butadiene of 1000g/mol and 50 kilograms of castor oil that 50 kilogram molecular weights are weighed
Alcohol is added in closed reactor, is warming up to 120 DEG C, is vacuumized while stirring, is stopped vacuumizing and heating after 2h, is cooled to 80
DEG C and 91.5 kilograms of trades mark are added is NPU(MX) Carbodiimide-Modified MDI(Cohan create company), the reaction was continued 2h is obtained
The performed polymer that NCO content is 22%.
The preparation of component A: 30 kilograms of polyester 2915(Si Taipan companies are weighed respectively), 30 kilograms of polyester 3050(Paasche supports
Company), 18 kilograms of castor oil polyhydric alcohols, 5 kilograms of 550D release agents (Technick Products company), 4 kilograms of high temperature
Totally 0.8 kilogram, 12 kilograms of 0.2 kilogram of FOMREZ UL-28 and 0.6 kilogram of K-5218 of 3A activated molecular sieve, the catalyst toasted
Talcum powder, 0.83 kilogram of ultraviolet absorbing agent benzotriazole and 0.66 kilogram of anti-aging agent thio-2 acid two (18) ester add
Enter into stirred tank and stirs evenly.
Component A and B component are directed respectively into bi-component in colloid system two storage tanks of corresponding A and B, glass fibre from
Creel forms certain tension through thread board under the drive of dragger, and with the speed of 250cm/min by being connected with two-component
For colloid system glue-injection box (two-component for colloid system injecting glue frequency be 1.6Hz, each injecting glue amount be 180g, B material with A expect weight
It than for 1.08:1), and is allowed to sufficiently infiltrate with AB component hybrid resin, into mold, (three area's temperature are respectively 200 DEG C, 180 DEG C
With 180 DEG C), resin curing molding and leaves mold at high temperature.
Mechanics Performance Testing: tensile strength is carried out according to composite material of the national standard GB/T 16421-1996 to preparation, is stretched
The test of modulus, elongation at break, bending strength and bending modulus.
Hydrolytic resistance test: the batten prepared according to above-mentioned standard is placed in the hydrothermal aging case of 85 DEG C and 85% humidity
1000h takes out and tests its mechanical property and down ratio.
Comparative example 1
Commercially available polyether-type dual-component polyurethane pultrusion resin
Component A and B component are directed respectively into bi-component in colloid system two storage tanks of corresponding A and B, glass fibre is from creel
Certain tension is formed under the drive of dragger through thread board, and with the speed of 150cm/min by being connected with two-component for glue
(two-component is 1.0Hz for colloid system injecting glue frequency to the glue-injection box of system, and each injecting glue amount is 120g, and B material is with A material weight ratio
1.25:1), and be allowed to sufficiently infiltrate with AB component hybrid resin, into mold (three area's temperature be respectively 160 DEG C, 180 DEG C and
150 DEG C), resin curing molding and leaves mold at high temperature.
Mechanics Performance Testing: tensile strength is carried out according to composite material of the national standard GB/T 16421-1996 to preparation, is stretched
The test of modulus, elongation at break, bending strength and bending modulus.
Hydrolytic resistance test: the batten prepared according to above-mentioned standard is placed in the hydrothermal aging case of 85 DEG C and 85% humidity
1000h takes out and tests its mechanical property and down ratio.
Comparative example 2
Commercial polyesters type dual-component polyurethane pultrusion resin
Component A and B component are directed respectively into bi-component in colloid system two storage tanks of corresponding A and B, glass fibre is from creel
Certain tension is formed under the drive of dragger through thread board, and with the speed of 150cm/min by being connected with two-component for glue
(two-component is 1.0Hz for colloid system injecting glue frequency to the glue-injection box of system, and each injecting glue amount is 120g, and B material is with A material weight ratio
1.05:1), and be allowed to sufficiently infiltrate with AB component hybrid resin, into mold (three area's temperature be respectively 160 DEG C, 180 DEG C and
150 DEG C), resin curing molding and leaves mold at high temperature.
Mechanics Performance Testing: tensile strength is carried out according to composite material of the national standard GB/T 16421-1996 to preparation, is stretched
The test of modulus, elongation at break, bending strength and bending modulus.
Hydrolytic resistance test: the batten prepared according to above-mentioned standard is placed in the hydrothermal aging case of 85 DEG C and 85% humidity
1000h takes out and tests its mechanical property and down ratio.
Performance data comparison between each embodiment and each comparative example:
From upper table data it can be seen that
The composite material that comparative example Examples 1 to 4 is prepared with comparative example 2(with commercial polyesters type dual-component polyurethane pultrusion resin)
Performance is substantially suitable, hence it is evident that the composite material prepared higher than comparative example 1(with commercially available polyether-type dual-component polyurethane pultrusion resin)；
After hydrolysis experiment, Examples 1 to 4 performance retention rate is apparently higher than comparative example 2, and performance retaining ratio is the same as comparative example 1
Quite.
Illustrate that compound polyurethane material prepared by the present invention has the mechanical strength of polyester resin based composites, simultaneously
The hydrolytic Resistance for having polyesther resins based composites.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
Claims (8)
1. a kind of preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials, which comprises the steps of:
Step S1, the preparation of B component hydrolysis Type Polyurethane Prepolymer takes out the polyalcohol with hydrophobic function at 120 DEG C
Vacuum 2h is cooled to 80 DEG C, and excessive Carbodiimide-Modified isocyanates is added, and reacts 2~3h, is had-NCO content
Base polyurethane prepolymer for use as；
Step S2, the preparation of component A polyol crosslink agent, each component and weight proportion are specific as follows:
55% ~ 80wt% of polyester polyol；
10% ~ 20wt% of vegetable oil polyol；
2% ~ 8wt% of release agent；
2% ~ 5wt% of deicer；
0.2 ~ 1wt% of catalyst；
0 ~ 25%wt% of filler；
0.5% ~ 1wt% of ultraviolet absorbing agent；
0.5 ~ 1wt% of anti-aging agent；
Step S3, two components in step S1 and step S2 are transferred to bi-component in 2 storage tanks of colloid system respectively；
Step S4, the continuous fiber for being soaked with resin is passed through into die material curing molding by dual-component polyurethane pultrusion system.
2. the preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials according to claim 1, feature exist
In the polyalcohol in the step S1 with hydrophobic function is castor oil polyhydric alcohol or molecular weight is 1000~2000g/mol's
One of end hydroxy butadiene polyalcohol；The anti-aging agent is 2,5- ditert-butylhydro quinone or thio-2 acid two
One of (18) ester.
3. the preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials according to claim 1, feature exist
In, in the step S1 finally be made performed polymer NCO content 15%~27%.
4. the preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials according to claim 1, feature exist
In vegetable oil polyol is castor oil polyhydric alcohol in the step S2；The deicer be 3A activated molecular sieve, using it is preceding
250 DEG C of baking 6h or more；The catalyst is delaying type catalyst；The filler is in calcium carbonate, aluminium hydroxide and talcum powder
One kind or in which several compositions；The ultraviolet absorbing agent is one of benzophenone or benzotriazole or in which several
The composition of kind.
5. the preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials according to claim 1, feature exist
In, two-component in the step S3 include A batch can, B batch can, two meterings being separately connected below AB batch can for colloid system
Pump and modules such as static mixer for mixing AB material, injecting glue frequency is 0.2~2Hz, and injecting glue amount is 50~200g/ times.
6. the preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials according to claim 1, feature exist
In, the dual-component polyurethane pultrusion system in the step S4 contain creel, feed carrier, glue-injection box, segmentally heating mold and
The modules such as dragger；Wherein, closed connected with glue-injection box for colloid system, segmentally heating mold is that 3rd area are heated, the first two area
Temperature range is 150~250 DEG C, and third area temperature range is room temperature~180 DEG C, and dragger draw-down rate is 10~280cm/
min。
7. the preparation method of hydrolysis resistant polyurethane pultrusion resin composite materials according to claim 1, feature exist
In the step S4 includes following four step:
The A material and B that S401, measured pump are got according to a certain percentage expect to enter dual-component polyurethane after static mixer mixes
In the closed glue-injection box of pultrusion system；
S402, the continuous fiber drawn from creel are through feed carrier, under the drive of dragger, with some tension and certain speed
It is sufficiently mixed and is infiltrated into glue-injection box, and with step S401 resin for getting to its inside；
S403, by the heating in mold leading portion and middle section, the continuous fiber through resin infiltration at the 2/3 of mold overall length or so,
Resin rapid curing at temperature and the collective effect of catalyst, is formed with the composite material of intensity；
Slight shrinkage can occur while S404, resin solidification, under the collective effect of release agent, in mold endpiece depanning.
8. a kind of hydrolysis resistant polyurethane pultrusion resin composite materials, which is characterized in that using in the claims 1~7
The polyurethane pultrusion resin composite materials that any one is prepared.
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| CN114591479A (en) * | 2022-04-18 | 2022-06-07 | 上海顺海精密机械有限公司 | Polyurethane system for preparing polyurethane pultrusion frame and preparation method thereof |
| CN114603883A (en) * | 2022-03-14 | 2022-06-10 | 丰城市晶科光伏材料有限公司 | Solar photovoltaic frame manufacturing device and method |
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