CN106867252B - Benzoxazine resin system for pultrusion and method for producing pultruded body therefrom - Google Patents
Benzoxazine resin system for pultrusion and method for producing pultruded body therefrom Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
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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
- B29C70/525—Component parts, details or accessories; Auxiliary operations
- B29C70/528—Heating or cooling
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a benzoxazine resin system for pultrusion, which comprises bicyclic benzoxazine, a filler, a curing agent, a release agent and an optional modified copolymer. The invention also provides a method for producing a pultrusion body by the benzoxazine resin system provided by the invention. The pultrusion body prepared by the benzoxazine resin system for pultrusion provided by the invention has excellent flame retardant property and mechanical property, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of pultrusion resin, and particularly relates to a benzoxazine resin system for pultrusion and a method for producing a pultrusion body by using the benzoxazine resin system.
Background
Pultrusion is one of the molding methods of thermosetting fiber reinforced composite materials, and can be used for producing profiles or other material products with fixed section shapes and unlimited length and width. The pultrusion process is that the continuous fiber dipped with resin glue solution is pulled out by a heating mould, and then the resin is further solidified by a heating chamber to prepare the continuous reinforced composite material section with unidirectional high strength. The pultrusion resin should meet the process requirements: the viscosity is low (less than 2.0Pa · s), and the wetting property is good; secondly, the curing shrinkage is low (various fillers can be added into the resin formula to reduce the shrinkage, improve the performance of the product and reduce the production cost); long gel time and short curing time; fourthly, the caking property is good; fifthly, the product has certain flexibility, and the formed product is not easy to crack.
Thermosetting resins used in the current pultrusion process mainly include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenolic resins, polyurethanes, and the like. However, these resins have some disadvantages, such as poor high temperature resistance or poor processability, and also have certain curing shrinkage, which affects the dimensional accuracy of the product, especially the current strict requirements on flame retardance, and most of the resins have poor flame retardance, and have limitations in application in some fields with special requirements. Therefore, there is a need for resins that simultaneously meet low viscosity, low cure shrinkage, long gel time, and short cure time.
Patent 201080054523.4 discloses a pultrusion system based on polyurethane, which has simple process, short curing time and fast speed, but can not be used in some fields due to the limitation of the performance of polyurethane, i.e. non-flame-retardant property, even if a corresponding flame retardant is added, the flame retardant property is improved, and the mechanical property and strength are linearly reduced. Patent 201110100751.7 discloses a pultrusion process and a pultrusion device for phenolic resin composite, which aims at the pultrusion of phenolic resin system, although the flame retardant property of the pultruded part is better, small molecules are released during the curing molding process, thereby affecting the mechanical property of the product.
Benzoxazine resin is a new thermosetting resin developed based on traditional phenolic resin. Compared with the traditional phenolic resin, the benzoxazine has the advantages of near-zero curing shrinkage, molecular designability, low water absorption, high carbon residue rate, ablation resistance and the like, is suitable for preparing fiber reinforced polymer matrix composite materials with low porosity and high performance, and has wide application prospects in the fields of buildings, aerospace, electronics and the like.
Therefore, there is a problem that research and development of a benzoxazine resin system for pultrusion and a method of producing a pultrusion product therefrom are urgently required.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a benzoxazine resin system for pultrusion, which comprises: bicyclic benzoxazines, fillers, curing agents, mold release agents, and optionally modified copolymers. The invention also provides a method for producing a pultrusion body by the benzoxazine resin system provided by the invention. The pultrusion body prepared by the benzoxazine resin system for pultrusion provided by the invention has excellent flame retardant property and mechanical property.
To this end, a first aspect of the present invention provides a benzoxazine resin system for pultrusion, comprising:
component a, a bicyclic benzoxazine;
component b, a filler;
component c, a curing agent;
component d, a release agent; and optionally
Component e, a modified copolymer.
According to the benzoxazine resin system, the benzoxazine resin system comprises the following components in parts by weight:
according to the benzoxazine resin system, the bicyclic benzoxazine comprises diamine benzoxazine shown in a general formula (I) and bisphenol benzoxazine shown in a general formula (II);
in the general formula (I), R1Is selected from C1-C10An alkylene group of,
One or more of (a). R2One or more selected from the group consisting of hydrogen and saturated or unsaturated hydrocarbon groups; preferably one or more selected from hydrogen, methyl, ethyl and vinyl.
In the general formula (II), R3Is selected from C1-C10An alkylene group of,
One or more of carbonyl, O, S. R4One or more selected from the group consisting of hydrogen and saturated or unsaturated hydrocarbon groups; preferably one or more selected from hydrogen, methyl, ethyl and vinyl.
The benzoxazine resin system provided by the invention adopts the dicyclic benzoxazine, and does not adopt monocyclic benzoxazine alone or a mixture of the monocyclic benzoxazine and the dicyclic benzoxazine, because the addition of the monocyclic benzoxazine can reduce the viscosity of the resin system, and the mechanical property and the flame retardance of the resin system are reduced accordingly.
In some embodiments of the present invention, the bicyclic benzoxazine is selected from one or more of phenol-diaminodiphenylmethane-type benzoxazine, bisphenol a-aniline-type benzoxazine, and bisphenol F-aniline-type benzoxazine.
In other embodiments of the present invention, the filler comprises one or more of a silicate, a sulfate, an oxide, a hydroxide, and carnauba wax. Preferably the silicate comprises talc and/or mica powder. Preferably the sulphate comprises barium sulphate and/or calcium sulphate. Preferably the oxide comprises alumina and/or silica. Preferably the hydroxide comprises magnesium hydroxide and/or aluminium hydroxide. The filler is particularly preferably carnauba wax, and the inventor finds that the addition of the carnauba wax has a lubricating effect, the resistance is reduced in the pultrusion process, the surface of the obtained product is bright, and a smooth protective film is formed on the surface of the product.
In other embodiments of the present invention, the curing agent comprises one or more of imidazole, diaminodiphenylmethane, oxalic acid and oxalic acid.
The modified copolymer of the present invention is an optional added component, preferably not added. The modified copolymer comprises one or more of epoxy resin, bismaleimide and phenolic resin.
The inventor of the invention researches and discovers that the addition of a small amount of modified copolymer can reduce the viscosity of a resin system to a certain extent and improve the mechanical property of a pultruded body, but the mechanical property is reduced on the contrary by adding excessive epoxy resin, and the flame retardant property of the pultruded body is reduced by adding the epoxy resin. According to the invention, the benzoxazine resin system without the modified copolymer is preferably selected, and the pultrusion product with excellent performances in all aspects is prepared by setting pultrusion process parameters, and the flame retardant property and the mechanical property are better than those of the benzoxazine resin system with the modified copolymer.
The term "optional" as used herein means either with or without, or with or without the addition of.
The raw materials used in the benzoxazine resin system according to the present invention are commercially available, unless otherwise specified.
In a second aspect, the present invention provides a method for producing a pultruded body, comprising: the benzoxazine resin system of the first aspect of the present invention is prepared by mixing the components, curing, demolding and pultrusion in a pultrusion machine.
In some embodiments of the invention, the mixing is performed at 100-130 ℃. In the pultrusion process, the mixing is carried out in a glue tank, namely the temperature of the glue tank is kept at 100-130 ℃, so that the problem of high pultrusion viscosity of the benzoxazine resin system is solved, the viscosity of the benzoxazine resin system can meet the requirement of gum dipping, the gum dipping effect is ensured, and the benzoxazine resin system can better soak glass fibers.
In other embodiments of the present invention, the pultrusion machine comprises a low temperature pre-heating zone, a medium temperature pre-forming zone, and a high temperature curing zone. Preferably, the temperature of the low-temperature preheating zone is 150-170 ℃; the temperature of the medium-temperature preforming zone is 180-195 ℃; the temperature of the high-temperature curing zone is 200-230 ℃.
In other embodiments of the present invention, the pultrusion speed is 130-200 mm/min.
The pultrusion process principle of the present invention is shown in figure 1. The twistless roving is led out from a creel 1, passes through a guide roller 2 and a yarn arranging device 3, is preheated by hot air, then enters a glue dipping tank 4, is dipped in a benzoxazine resin system mixture, and then enters a mould 5 for molding and curing. After curing is completed, the product is drawn by a drawing device 6 and cut 7 to obtain the required pultruded product.
The invention has the beneficial effects that:
the resin system containing the dicyclic benzoxazine, the filler, the curing agent, the release agent and the optional modified copolymer has the characteristics of good wettability, long gel time, short curing time, no release of small molecules in the curing process, low curing shrinkage rate of resin and the like in pultrusion impregnation. In addition, the obtained pultrusion body has the advantages of excellent mechanical property, high temperature resistance, smooth surface of a workpiece, low hygroscopicity, excellent flame retardant property and the like. The pultrusion body has higher carbon residue rate at high temperature and can be used for a long time at the temperature of 150 ℃ to 200 ℃.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of the pultrusion process. The reference numerals in the figures have the following meanings:
1-a creel; 2-a guide roll; 3-a creel device; 4-a glue dipping tank; 5-molding; 6-a traction device; 7-cutting.
Detailed Description
The invention will be further described with reference to the following figures and examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
The performance test method of the pultruded body obtained by the invention comprises the following steps:
(1) mechanical properties
Tensile strength: reference standard GB-T1447-;
bending strength: the bending property test method of the fiber reinforced plastic is referred to the GB-T1449-;
compressive strength: refer to the compression performance test method of GB-T1448-.
(2) Flame retardant properties
LOI (limiting oxygen index): reference is made to the oxygen index method of the test method of the combustion performance of the fiber reinforced plastic in GB-T8924-.
UL-94 rating: UL-94 vertical burn test.
Example 1
(1) Preparation of benzoxazine resin system mixtures
Adding 80 parts of phenol/diaminodiphenylmethane benzoxazine into 20 parts of bisphenol F epoxy resin, uniformly mixing at 120 ℃, then adding 2 parts of a release agent, sequentially adding 2 parts of carnauba wax, 5 parts of talcum powder, 10 parts of magnesium hydroxide and 1 part of imidazole after uniformly mixing, and preparing the benzoxazine resin system mixture after uniformly mixing.
(2) Production of pultruded bodies
And starting the glass fiber drying equipment, drying the moisture of the glass fiber, and starting to penetrate the yarns into the die to ensure that the yarns are uniformly distributed in the die. After the yarns are threaded, adjusting the level of the die, opening the glue tank for heating, and setting the temperature of the glue tank to be 100 ℃. The mold heating device was started and the mold temperatures were set to 160 ℃ in the first zone (low temperature preheating zone), 185 ℃ in the second zone (medium temperature preforming zone) and 210 ℃ in the third zone (high temperature curing zone). And (4) after the mold reaches a set temperature and is kept warm for a period of time, adding the mixed benzoxazine resin system into the glue groove. Then, pultrusion was carried out, setting the pultrusion speed at 150 mm/min. The results of the performance tests of the obtained pultruded body are shown in Table 1.
Example 2
(1) Preparation of benzoxazine resin system mixtures
Adding 90 parts of bisphenol A-aniline benzoxazine into 10 parts of bisphenol A epoxy resin, uniformly mixing at 120 ℃, then adding 2 parts of a release agent, sequentially adding 2 parts of carnauba wax, 5 parts of fumed silica, 12 parts of magnesium hydroxide and 1 part of imidazole after uniform mixing, and preparing a benzoxazine resin system mixture after uniform mixing.
(2) Production of pultruded bodies
And starting the glass fiber drying equipment, drying the moisture of the glass fiber, and starting to penetrate the yarns into the die to ensure that the yarns are uniformly distributed in the die. After the yarns are threaded, adjusting the level of the die, opening the glue tank for heating, and setting the temperature of the glue tank to be 120 ℃. And (3) starting a mold heating device, setting the temperature of the mold to be 150 ℃ in a first area (low-temperature preheating area), 180 ℃ in a second area (medium-temperature preforming area and 200 ℃ in a third area (high-temperature curing area), keeping the temperature for a period of time, adding a mixed benzoxazine resin system into a glue groove, performing pultrusion, and setting the pultrusion speed to be 130mm/min, wherein the performance test result of the obtained pultrusion body is shown in table 1.
Example 3
(1) Preparation of benzoxazine resin system mixtures
Adding 60 parts of bisphenol A-aniline benzoxazine into a mixture of 15 parts of phenolic novolac resin and 5 parts of bisphenol F epoxy resin, uniformly mixing at 120 ℃, then adding 2 parts of a release agent, sequentially adding 2 parts of carnauba wax, 5 parts of silicon dioxide, 5 parts of mica powder and 1 part of imidazole after uniform mixing, and preparing a benzoxazine resin system mixture after uniform mixing.
(2) Production of pultruded bodies
And starting the glass fiber drying equipment, drying the moisture of the glass fiber, and starting to penetrate the yarns into the die to ensure that the yarns are uniformly distributed in the die. After the yarns are threaded, adjusting the level of the mold, starting the glue tank for heating, setting the temperature of the glue tank to be 130 ℃, starting the mold heating device, setting the temperature of the mold to be 170 ℃ in a first area (a low-temperature preheating area), 185 ℃ in a second area (a medium-temperature preforming area and 220 ℃ in a third area (a high-temperature curing area), keeping the temperature for a period of time, adding a mixed benzoxazine resin system into the glue tank, then performing pultrusion, setting the pultrusion speed to be 200mm/min, and obtaining the performance test result of the pultrusion formed body shown in table 1.
Example 4
(1) Preparation of benzoxazine resin system mixtures
Adding 2 parts of release agent into 100 parts of bisphenol F-aniline benzoxazine at 120 ℃, mixing uniformly, then adding 2 parts of carnauba wax, 5 parts of silicon dioxide, 5 parts of mica powder and 1 part of curing agent in sequence, and mixing uniformly to obtain the benzoxazine resin system mixture.
(2) Production of pultruded bodies
And starting the glass fiber drying equipment, drying the moisture of the glass fiber, and starting to penetrate the yarns into the die to ensure that the yarns are uniformly distributed in the die. After the yarns are threaded, adjusting the level of the die, opening the glue tank for heating, and setting the temperature of the glue tank to be 130 ℃. Starting a mold heating device, setting the temperature of the mold to be 170 ℃ in a first area (a low-temperature preheating area), 195 ℃ in a second area (a medium-temperature preforming area and 230 ℃ in a third area (a high-temperature curing area), keeping the temperature for a period of time, adding a mixed benzoxazine resin system into a glue tank, performing pultrusion, and setting the pultrusion speed to be 200mm/min, wherein the performance test result of the obtained pultrusion body is shown in table 1.
Comparative example 1
(1) A resin system mixture was prepared as in example 1, except that the benzoxazine was replaced with an epoxy resin.
(2) The pultruded body was prepared as in example 1. The results of the performance tests of the obtained pultruded body are shown in Table 1. Comparative example 2
(1) A resin system mixture was prepared as in example 1, except that the benzoxazine was replaced with a phenolic resin.
(2) The pultruded body was prepared as in example 1. The results of the performance tests of the obtained pultruded body are shown in Table 1.
Comparative example 3
(1) A resin system mixture was prepared as in example 1, except that the benzoxazine was replaced with a polyurethane resin.
(2) The pultruded body was prepared as in example 1. The results of the performance tests of the obtained pultruded body are shown in Table 1. Comparative example 4
(1) A resin system mixture was prepared as in example 1, except that 100 parts of bisphenol F-aniline type benzoxazine was replaced with a mixture of 35 parts of phenol-aniline type benzoxazine, 35 parts of diphenylmethane diamine type benzoxazine and 30 parts of epoxy resin.
(2) The pultruded body was prepared as in example 1. The results of the performance tests of the obtained pultruded body are shown in Table 1.
TABLE 1 Properties of the pultruded body
As can be seen from Table 1, compared with comparative examples 1 to 4, the pultruded bodies prepared in the examples of the present invention have a higher LOI value, and the UL-94 ratings are all V0 grades, having good flame retardant properties; meanwhile, the pultrusion body has high tensile strength, bending strength and compression strength and good mechanical property.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (9)
1. A method of producing a pultruded body comprising: mixing the components of the benzoxazine resin system, and then curing, demoulding and pultrusion in a pultrusion machine to prepare the pultrusion body; the mixing is carried out at the temperature of 100-130 ℃; the pultrusion machine comprises a low-temperature preheating zone, a medium-temperature preforming zone and a high-temperature curing zone; the temperature of the low-temperature preheating zone is 150-170 ℃; the temperature of the medium-temperature preforming zone is 195 ℃; the temperature of the high-temperature curing area is 230 ℃; the pultrusion speed is 130-200 mm/min;
the benzoxazine resin system comprises the following components in parts by weight:
the benzoxazine resin system does not comprise a modifying copolymer;
the modified copolymer comprises one or more of epoxy resin, bismaleimide and phenolic resin.
2. The method according to claim 1, wherein the bicyclic benzoxazines comprise diamine-type benzoxazines represented by general formula (I) and bisphenol-type benzoxazines represented by general formula (II);
in the general formula (I), R1Is selected from C1-C10An alkylene group of,
One or more of; r2One or more selected from the group consisting of hydrogen and saturated or unsaturated hydrocarbon groups;
in the general formula (II), R3Is selected from C1-C10An alkylene group of,
One or more of carbonyl, O, S; r4One or more selected from hydrogen and saturated or unsaturated hydrocarbon groups.
3. The method of claim 2, wherein C is1-C10Alkylene of (A) is
4. The method of claim 1, wherein the filler comprises one or more of a silicate, a sulfate, an oxide, a hydroxide, and carnauba wax.
5. The method according to claim 4, wherein the silicate comprises talc and/or mica powder.
6. A method according to claim 4, wherein the sulphate comprises barium sulphate and/or calcium sulphate.
7. The method of claim 4, wherein the oxide comprises alumina and/or silica.
8. The method of claim 4, wherein the hydroxide comprises magnesium hydroxide and/or aluminum hydroxide.
9. The method of claim 1, wherein the curing agent comprises one or more of imidazole, diaminodiphenylmethane, and oxalic acid.
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| CN113248865B (en) * | 2021-05-10 | 2023-10-27 | 泰安市中研复合材料科技有限公司 | Benzoxazine resin system capable of being rapidly cured and composite material |
| CN114015194B (en) * | 2021-10-19 | 2023-10-20 | 航天特种材料及工艺技术研究所 | Polybenzoxazine aerogel and preparation method thereof |
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| CN104254566A (en) * | 2011-09-30 | 2014-12-31 | 吉坤日矿日石能源株式会社 | Benzoxazine resin composition, and fiber-reinforced composite material |
| CN103834168A (en) * | 2014-02-25 | 2014-06-04 | 广东生益科技股份有限公司 | Halogen-free flame retardant type resin composition |
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