CN100467509C - Method for preparing normal temp solidified high stvength glass fire reinforced plastics - Google Patents

Method for preparing normal temp solidified high stvength glass fire reinforced plastics Download PDF

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Publication number
CN100467509C
CN100467509C CNB021355576A CN02135557A CN100467509C CN 100467509 C CN100467509 C CN 100467509C CN B021355576 A CNB021355576 A CN B021355576A CN 02135557 A CN02135557 A CN 02135557A CN 100467509 C CN100467509 C CN 100467509C
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China
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preparation
resol
reaction
stirring
reinforced plastics
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CN1483749A (en
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刘继广
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Shandong Analysis and Test Center
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Shandong Analysis and Test Center
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Abstract

The present invention provides a preparation method of normal temp. solidified high-strengthu glass fibre reinforced plastics, including preparation of phenolic resin, preparation of modification solidifying agent and preparation of modified phenolic resin glass fibre reinforced plastics. It is characterized by that the phenolic resin and modification solidifying agent are mixed under the action of catalyst, and solidified at normal temp., then can be used for making various phenolic resin glass fibre reinforced plastics products.

Description

A kind of preparation method of normal temp solidified high stvength glass fire reinforced plastics
1, technical field
The present invention relates to a kind of preparation method of organic materials, specifically a kind of preparation method of normal temp solidified high stvength phenolic fiberglass reinforced plastics.
2, technical background
Fibre resins such as glass fibre, carbon fiber, nylon fiber dipping is bonding, can be made into various fiber reinforcement type matrix materials or equipment, because this kind matrix material has the favorable mechanical performance, so be widely used in every field such as building, communications and transportation, aviation, electric, mine, chemical industry equipment, military affairs, wherein the matrix material made of fiber has the title of glass reinforced plastic again.The resin that is generally used for bonding infiltration fiber has epoxy, polyester, phenolic aldehyde, PVC etc., wherein resol and Resins, epoxy are widely used as thermosetting resin, and especially resol is subjected to people's favor especially with its good thermotolerance and excellent flame-retardant performance.
The curing that it is resol that yet traditional resol is made the existing in actual applications deficiency of technology of fibre glass product manufacture often will just can be carried out under the condition of High Temperature High Pressure, so forming technique mainly relies on mould pressing process, in glass fiber reinforced plastics product making processes,, thereby have a strong impact on the use range of phenolic aldehyde goods and the performance of product because resol will add a large amount of solvents reducing the viscosity of resin before curing.The restriction of its processing condition has seriously restricted the development of phenolic resin composite.Thereby development low-temperature curing resol becomes the matter of utmost importance of the sector.
U.S. Pat 4 053,447 have disclosed a kind of Resorcinol modified phenolic resins, can ambient cure, yet need when solidifying, need add the Paraformaldehyde 96 powder to realize ambient cure, this has greatly toxic to the user, though the Resorcinol modified phenolic resins can be used for low-temperature curing, need to add a large amount of solvents and just can be used to soak into fiber to reduce viscosity.Solvent still can produce bubble in the reaction process of resin, stay pin hole after the curing, has had a strong impact on the intensity of product.U.S. Pat 5075,413 and US 5 075,414 also discloses a kind of Resorcinol and formaldehyde at first forms the initial stage product in addition, and then mix with another resol and to use to prepare the method for organic resin fibre composite.But it still need add methyl donors such as furfural, propenal quicken to solidify and to reduce viscosity in resol, this class donor has peculiar smell volatile and poisonous, as health aldehyde peculiar smell is arranged and solidify after product is turned black, propenal has severe toxicity.And still contain a large amount of water in the initial stage product of Resorcinol that uses as solidifying agent and formaldehyde, and equally can stay pin hole in the goods after curing, reduced the performance of goods.
3, summary of the invention
The present invention discloses a kind of preparation method of normal temperature solidified high-strength phenolic resin and the method that impregnated glass fiber normal temperature prepares fibre composite.
The preparation method of normal temp solidified high stvength phenolic fiberglass reinforced plastics of the present invention, comprise the preparation of resol, the preparation of the preparation of modified firming agent and modified phenolic resins fibre glass product manufacture, normal temperature solidifies down and is used for various phenolic resin frp goods and makes under the existence that is blended in catalyzer with the resol and the modified firming agent of phenol and Paraformaldehyde 96 or prepared formaldehyde.
In the preparation method of normal temp solidified high stvength glass fire reinforced plastics of the present invention, the preparation of resol is to adopt phenol and Paraformaldehyde 96 to react in the ratio of the molar ratio 1:1.1-3.5 of material reaction to make, phenol is put into the container that has agitator and thermometer, stirring is warming up to 80 ℃-120 ℃, add catalyzer and add Paraformaldehyde 96 while stirring, insulation reaction, reach 200-800MPa.S until viscosity, it is standby that last vacuum hydro-extraction gets light yellow resol, and the ratio of reaction mass preferably is controlled at 1:1.5-2.5.
In the preparation method of normal temp solidified high stvength glass fire reinforced plastics of the present invention, it is that ratio reaction in the molar ratio 1:1.1-3.5 of material reaction makes that the preparation of resol can be adopted phenol and formaldehyde, phenol is put into the container that has agitator and thermometer, stirring is warming up to 80 ℃-120 ℃, add catalyzer and add formaldehyde while stirring, insulation reaction reaches 200-800MPa.S until viscosity, and it is standby that last vacuum hydro-extraction gets light yellow resol.The ratio of this reaction mass preferably is controlled at 1:2.5.
In the preparation method of normal temp solidified high stvength glass fire reinforced plastics of the present invention; the preparation of modified firming agent is to make with the mixed reaction by the mol ratio 1:1-3 of reaction mass of Resorcinol and acyl compounds or Resorcinol and anhydride compound; in proportion Resorcinol is added in the retort that has stirring and thermometer; add anhydride compound or acyl compounds while stirring; be warming up to 60-90 ℃, react standby after the underpressure distillation dehydration after 10 minutes.The ratio of reaction mass preferably is controlled at 1:2.
Its molecular formula of employed carboxylic acid halides is RCOX in the modified firming agent preparation feedback; The molecular formula of anhydride compound is (RCO) 2O, the R in acetyl halide compound and the anhydride compound molecular formula is CnH2n+1 or CnHn-1, n=1-18, the X in the acyl group molecular formula are chlorine Cl, bromine Br and iodine I.
The catalyzer of reactive modified phenolic resin can be selected NaOH, Na for use 2CO 3, zinc acetate or ammoniacal liquor one or more mixture; Modified solidified catalyst for reaction can be used organic acid or mineral acid HCl, H such as Whitfield's ointment, tosic acid, oxalic acid 3PO 4, H 2SO 4, HBF 4, HClO 4One or more mixture, modified solidified catalyst for reaction can add in the component of solidifying agent in advance, also can add when modified firming agent and reactive modified phenolic resin, the adding proportion of catalyzer is 1-40% of a reaction mass gross weight; The adding proportion of catalyzer preferably is controlled at 10-20%.
Modified firming agent is to have very low viscous liquid among the present invention, is easy to use and the normal temperature hand pasting forming, and the solvent or the thinner that need not to add any component reduce viscosity.
The resol that adopts optimization technology to obtain among the present invention has lower viscosity and high solids content, can directly mix to use with modification Resorcinol modified component need not to add solvent to reduce viscosity, also can normally use if add solvent.This resin also has less content of free aldehyde, and burst size of methanal is seldom arranged when solidifying.
This invention is owing to adopt the phenolic resin modified Resorcinol component of high reactivity high solids content all to participate in reaction when solidifying, so the phenolic aldehyde goods that form have hole still less, flexural strength increases by 90% and has better mechanical property.
Because the two components in this invention all have lower viscosity,, help hand paste technology and ambient cure and prepare fibre composite so can directly be used for sized glass fibres easily.
Fiber also can adopt glass fibre in this invention, carbon fiber, nylon and other filamentary material.
Resin in this invention also can be used to casting, can dose mineral filler during use, as compositions such as clay, hydrochlorinate magnesium, barium sulfate, divides curing molding in order to glass fiber reinforced plastics product.
5, embodiment
Embodiment one,
The preparation of modified firming agent: take by weighing Resorcinol (95%) 550 gram, add have stir and the retort of thermometer in, add 700 gram Acetyl Chloride 98Min.s while stirring, react completely, gas is removed in decompression, adds oxalic acid 15 and restrains, continue to be stirred to react completely standby.
The preparation of resol: take by weighing phenol 470 grams, add in the retort that has stirring and thermometer, stirring is warming up to more than 90 ℃, add 5 gram zinc acetate and water, stirring adds 300 gram Paraformaldehyde 96s, insulation reaction gradually, reach 200-800MPaS until viscosity, vacuum hydro-extraction gets light yellow resin.
Embodiment two,
The preparation of resol: take by weighing phenol 500 grams, adding has in the reaction vessel of agitator and thermometer, stirs and is warming up to 90 ℃, add 5 gram sodium hydroxide, stir formaldehyde solution 900 grams of adding 37%, back flow reaction is after 5 hours, vacuum is anhydrated, and adds acid and transfers pH value to neutral.
The preparation of modified firming agent: take by weighing Resorcinol (95%) 560 gram, put into the retort that has stirring and thermometer, add 900 gram diacetyl oxides while stirring, heat up 90 ℃, react and cooled off standby in 1 hour.
Embodiment three,
The preparation of phenolic resin frp goods, resol and modified firming agent are pressed the mixed of 1:5, adopt the manual brushing woven fiber glass to prepare the phenolic resin frp goods that thickness is 2mm, ambient cure 0.5-48 hours then.
1, in the preparation method of normal temp solidified high stvength glass fire reinforced plastics of the present invention, use the resol and the solidifying agent of embodiment 1 preparation, the 0.14mm plain weave glass wool cloth that uses Shanghai credit China no alkali fiber company limited to produce, consumption is 49%.
The performance test results of solidifying back glass reinforced plastic is as follows:
Tensile strength 240MPa
Flexural strength 270MPa
Bending elastic modulus 12.9GPa
Oxygen index: 55%
This galss fiber reinforced resin matrix material has higher physical strength and good flame retardant property as seen from the above table.
2, in the preparation method of normal temp solidified high stvength glass fire reinforced plastics of the present invention, use the resol and the solidifying agent of embodiment 2 preparations, add the tosic acid of amount of resin 1%, the 0.14mm plain weave glass wool cloth that uses Shanghai credit China no alkali fiber company limited to produce, consumption is 50%.
The performance test results of solidifying back glass reinforced plastic is as follows:
Tensile strength 240MPa
Flexural strength 260MPa
Bending elastic modulus: 11.7GPa
Oxygen index 54%
By above detection data as can be known, the solidifying agent of use different material preparation and resol are in the presence of different catalysts, and the gained result distinguishes not quite, has mechanical property and good flame retardant resistance preferably.
The preparation method of a kind of normal temp solidified high stvength phenolic fiberglass reinforced plastics of the present invention and prior art are mutually Ratio, have that technological design is reasonable, easy to operate, easy to use, curing agent is solvent-free, viscosity is low, The characteristics such as solid content height, normal temperature cure, good flame resistance, mechanical strength height, the scope of application are wide, because of And, have good value for applications.

Claims (3)

1. the preparation method of a normal temp solidified high stvength glass fire reinforced plastics, comprise the preparation of resol, the preparation of the preparation of modified firming agent and modified phenolic resins fibre glass product manufacture, it is characterized in that under the existence that resol and modified firming agent with phenol and Paraformaldehyde 96 or prepared formaldehyde be blended in catalyzer that normal temperature solidifies down is used for various phenolic resin frp goods and makes, and preparation process is as follows:
The preparation of a, resol is to make by the reaction of the molar ratio of phenol and polyformaldehyde reaction material 1:1.1-3.5, phenol is put into the container that has agitator and thermometer, stirring is warming up to 80 ℃-120 ℃, add catalyzer and add Paraformaldehyde 96 while stirring, insulation reaction, reach 200-800MPa.S until viscosity, it is standby that last vacuum hydro-extraction gets light yellow resol;
Or adopt phenol and formaldehyde to react to make by the molar ratio of reaction mass 1:1.1-3.5, phenol is put into the container that has agitator and thermometer, stirring is warming up to 80 ℃-120 ℃, add catalyzer and add formaldehyde while stirring, insulation reaction, reach 200-800MPa.S until viscosity, it is standby that last vacuum hydro-extraction gets light yellow resol;
The preparation of b, modified firming agent is to make with Resorcinol and acyl compounds or with the mixed reaction by the mol ratio 1:1-3 of reaction mass of Resorcinol and anhydride compound; in proportion Resorcinol is added in the retort that has stirring and thermometer; add anhydride compound or acyl compounds while stirring; be warming up to 60-90 ℃, react standby after the underpressure distillation dehydration after 10 minutes.
2. the preparation method of a kind of normal temp solidified high stvength glass fire reinforced plastics according to claim 1 is characterized in that employed acyl compounds in the modified firming agent preparation feedback, and its molecular formula is RCOX; The molecular formula of anhydride compound is (RCO) 2O, the R in acyl compounds and the anhydride compound molecular formula is C nH 2n+1Or C nH N-1, n=1-18, the X in the acyl group molecular formula are chlorine Cl, bromine Br and iodine I.
3. the preparation method of a kind of normal temp solidified high stvength glass fire reinforced plastics according to claim 1, the catalyzer adding proportion that it is characterized in that reactive modified phenolic resin is controlled at 0.1-10%, and the adding proportion of the catalyzer of curing reaction is 1-40% of a reaction mass total amount.
CNB021355576A 2002-09-20 2002-09-20 Method for preparing normal temp solidified high stvength glass fire reinforced plastics Expired - Fee Related CN100467509C (en)

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Publication number Priority date Publication date Assignee Title
CN101831042B (en) * 2010-05-27 2012-07-04 西北工业大学 Preparation method of thermoplastic phenolic resin with high solid content
CN103694628B (en) * 2013-12-31 2015-12-02 山东圣泉新材料股份有限公司 A kind of preparation method of glass reinforced plastic

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