JPS5968336A - Production of glass fiber-reinforced plastics having excellent resistance to corrosion by acid at high temperature - Google Patents

Abstract

PURPOSE:To obtain the titled FRP, by impregnating a glass fiber-reinforced substrate with a compsn. consisting of an epoxy polyacrylate resin, a polyacrylate resin, a diallyl terephthalate resin and a hardener and curing it. CONSTITUTION:20-80pts.wt. diallyl terephthalate, 0-30pts.wt. styrene, 0.5- 5pts.wt. ketone peroxide and/or alkyl peroxy ester, 0.1-2pts.wt. cobalt salt of an org. acid and/or vanadium salt of an org. acid and 0.01-0.1pts.wt. tertiary amine are blended with 100pts.wt. mixture consisting of 50-80wt% epoxy polyacrylate resin and 50-20wt% bisphenol type or novolak type polyacrylate resin. 80-10pts.wt. glass fiber-reinforced substrate is impregnated with 20-90wt% said resin compsn. and cured.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glass fiber reinforced plastics (F RP ) having excellent acid corrosion resistance, particularly at high temperatures.

FRP as an industrial material is gradually being used in various industrial fields due to its processability and economic efficiency. It is. However, as the uses of FRP expand, FRP has properties that cannot be satisfied with the above resins, such as heat resistance and corrosion resistance.
As a result, epoxy polyacrylate resin was developed as a resin that satisfies these demands.

Its applications are wide-ranging even in the fields where corrosion resistance is particularly required as mentioned above, especially for materials used in flues, chimneys, tacts, etc. of waste gas treatment facilities that are in contact with high-temperature atmospheres of 100°C or higher. For example, conventional metal materials are exposed to various corrosive substances such as inorganic acids that have reached acid dew points, chlorine scum, nitrogen oxides, and organic substances. Of course, even FRP made from the above-mentioned epoxy polyacrylate resin was not sufficient as a material that could withstand such an environment.

The present inventors have conducted research on impregnating resins containing epoxy polyacrylate resin as a main component in order to obtain FRP that can withstand use under severe environmental conditions such as those described above. A composition consisting of a specific ratio of a resin, a bisphenol type or novolac type polyacrylate resin, and diallyl terephthalate has excellent room temperature curability, and by using this as an impregnation resin, an FRP that can withstand the above environment can be obtained. I found out that it is necessary. Most importantly, conventional odor-C is also highly polymerizable to epoxy polyacrylate resin.
Compositions containing diallyl orthophthalate or diallyl isophthalate are known. However, diallyl terephthalate, which is one of the isomers of diallyl phthalate-1~, is surprisingly particularly effective as a component of the resin composition of the present invention, and furthermore, it has been found that diallyl terephthalate, which is one of the isomers of diallyl phthalate-1~, is particularly effective as a component of the resin composition of the present invention. It was not known at all that a resin composition with a specific blending ratio had a remarkable effect on corrosion resistance at high temperatures, which cannot be obtained with conventional FRP, and the present inventors discovered this for the first time. That's what happened.

That is, in the present invention, (C) diallyl terephthalate is added to 100 parts by weight of a resin consisting of (a) 50 to 20% by weight of an epoxy polyacrylate resin and (b) 50 to 20% by weight of a bisphenol type or novolac type polyacrylate resin. 20-80 parts by weight, (d) styrene 0-30
Weight part.

(e) 0.5 to 5 parts by weight of ketone peroxide and/or alkyl peroxy ester, (f) 0.1 to 2 parts by weight of organic acid salt of cobalt and/or organic acid salt of vanadium, and (g) third 20 to 90% by weight of a resin composition containing 0.01 to 0.1 parts by weight of class amines was added to a glass fiber reinforced base material of 80% by weight.
The present invention provides a method for producing FRP having excellent acid corrosion resistance at high temperatures, which is characterized by impregnating the FRP at a concentration of up to 10% and curing it.

The epoxy polyacrylate-1-resin used in the present invention is a reaction product of an epoxy resin and (meth)acrylic acid, and usually has a (meth)
It is produced by reacting 0.8 to 1.2 moles of acrylic acid in the presence of a catalyst such as triethylamine and a polymerization inhibitor such as hydroquinone at a reaction temperature of 80 to 160°C. Epoxy resins have two or more epoxy groups in their molecules, such as bisphenol-type epoxy resins and novolac-type epoxy resins.

The polyacrylate resin used in the present invention is an additive reaction product of a polyphenol such as hisphenol or novolac and an alkylene oxide. This is a polyacrylate resin obtained.A specific example of such a polyacrylate resin is (2゜2-
his(4-(2-acryloxyethoxy)phenyl)propane, 2,2-bis(4-(2-< 2-acryloxyethoxy)ethoxy)phenyl)propane, 2,2
-bis[4-(2-acryloxypropoxy)phenyl]propane, 2,2-bis(4-(2-methacryloxyethoxy)phenyl)propane, 2゜2-bis(4-(
2-(2-methacryloxyethoxy)ethoxy)phenyl]propane, 2,2-his(4-(2-methacryloxypropoxy)phenyl)propane, 2,2-bis(4
-(3-methacryloxypropoxy)phenyl]propane, 2,2-bis[4-(2-(2-(2-acryloxyethoxy)ethoxy)■1~xy]phenyl]propane and oxyethylated novolak or oxy Examples include poly(meth)acrylate of propylenated novolak.

In the present invention, the ratio of the resin components consisting of (a>, (b), and (c)) is (a) 50 to 80% by weight of resin to boxy polyacrylate I and (b) bisphenol type or novolak type polyacrylate. Diallyl terephthalate (C) is used in an amount of 20 to 80 parts per 10 parts by weight of a mixture consisting of 50 to 20% by weight of the resin.If the content of component (a) is less than 50% by weight, the room temperature curability becomes poor and the initial physical properties deteriorate. Also, if component (b) is less than 20% by weight, that is, component (a), epoxy polyacrylate 1 to
When the resin exceeds 80% by weight, the viscosity of the resin component becomes too high, and depending on the specified amount of component (C) and the blend of component (1), the practical viscosity cannot be reached. This results in poor workability.

If the amount of component (c) is less than 20 parts by weight per 100 parts by weight of both components (a) and (b), it will not be possible to provide sufficient high-temperature acid corrosion resistance, which is the objective of the present invention, and the resin composition will be The viscosity of the product increases and the workability deteriorates. (C)
If the amount of the component exceeds 80 parts by weight, room temperature curability deteriorates.

If necessary, styrene as U(d) component may be added as a viscosity adjusting diluent to the resin component of the present invention in an amount of 30 parts by weight or less per 100 parts by weight of components (a) and (b). can. Addition of more than 30 parts by weight is not preferable because it significantly reduces the effects of the present invention.

The curing catalyst of the composition of the present invention includes an organic peroxide consisting of ketone peroxide, alkyl peroxy ester, or a mixture thereof, a curing accelerator consisting of cobalt or vanadium, or a mixture thereof; A room-temperature curing curing catalyst system composed of a curing accelerator of tertiary amines is used.

When the above organic peroxide is used as a mixed system, the ratio of ketone peroxide and alkyl peroxy ester is 1:1 to 1:10 by weight, preferably 1:4 to 1:
It is recommended to use it within the range of 8. Examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, and the like.

Examples of alkyl peroxy esters include tert-butyl perbenzoate, tert-butyl peroxyocl-ate, and tert-butyl peroxy-2-ethylhexoate.

Tert-butyl peroxy-3,5,5-1 to rimedylhexoate, tert-butyl peroxy acetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy bivalate, tert-butyl peroxy isopro Examples include vinyl carbonate, di-tert-butyl peroxy adipate, and the like.

When the above curing accelerator is used in a mixed system, Kobal 1 to
The mixing ratio of the organic acid salt and the vanadium organic acid salt is preferably in the range of 10:1 to 1:1 in terms of weight ratio calculated as metal. The above-mentioned 1aM M preferably has 6 to 12 carbon atoms, and metal salts of octenoic acid or naphthenic acid are particularly preferably used.

Examples of the tertiary amines that are the curing accelerator C are:
Dimethylaniline, diethylaniline, dimethyltoluidine, jetanolaniline, phenylmorpholine, triethylamine, tributylamine, methylmorpholine.

Examples include piperidine and triethylenediamine.

The amount of these curing catalysts to be used is determined based on the total resin content of the epoxy polyacrylate resin as the component (a) and the bisphenol type or novolak type polyacrylate resin as the component (b) of the composition of the present invention. Oxide 0.
A range of 5 to 5 parts by weight, 0.1 to 2 parts by weight of the curing accelerator, and 0.01 to 0.1 parts by weight of the curing accelerator is preferable in terms of processability and properties of the cured product. When the curing catalyst of the present invention is used, the curing of the resin can proceed even at around 0° C., and the characteristics of the present invention can be exhibited, making it possible to perform on-site construction in winter, which is very advantageous. When rapid curing is required, it is desirable to perform after-curing by heating.

The forms of the glass fibers that are the reinforcing base material used in the present invention include strands, chopped strands, and chopped strands.

Surface pine 1~. There are swirl mats, rovings, crow cloths, etc., and these are selected depending on the use of FRP and the molding method. Further, in addition to the above-mentioned glass fibers, carbon fibers and organic fibers can be used in combination as necessary.

The ratio of the resin composition and the glass fiber reinforced base material in the FRP of the present invention is 20 to 90% by weight for the former and 80% for the latter.
A range of 10% by weight is suitable. The first resin composition is 2
If it is less than 0%, the adhesion with the reinforcing base material will be insufficient, resulting in a significant decrease in mechanical strength (this will result in poor heat resistance and acid corrosion resistance. If it is less than %, the reinforcing effect will be small and the FRP will not have sufficient strength for use.

The molding method may be a conventional FRP molding method, such as a well-known method such as hand-lay azzo? methods such as spray-up method, filament winding method, and centrifugal molding method are used.

The FRP obtained by the present invention is particularly useful as members that require corrosion resistance, such as flues, chimneys, and ducts in waste gas treatment facilities, as well as pipes and tanks connected to chemical reaction equipment. The present invention will be explained below with reference to Examples.

Examples 1 to 6, Comparative Examples 1 to 6 -U, ll5K-69 using the resin compositions shown in Table 1
A test piece was produced according to the method for producing a laminate test piece specified in No. 19. The glass fiber used was Surface Mat (
S) (Nitto Boseki IU rMs-30WJ) and chopped strand mat (M) (Nitto Boseki rMC-45
0CJ), the configuration of the laminate is 5M3S'r test piece size is 130X 100X 39, resin composition content is 70
Weight% C.

The obtained test piece was placed on the inner wall of a stainless steel rectangular dow measuring 1.6 m long and 2.0 m wide. After 6 months.

After 12 months, each physical property was measured based on JISK-6919, the retention rate for the initial physical property was determined, and the results were used for the first
Shown in the table. Test conditions are exhaust gas temperature 120'C~1
SOx O at 50℃, Futan 2x 10'Nm'/hr
,1%, NOx 200Dll1m, 8201
The waste gas contained 0%. During the test period, the surface of the test piece was always covered with agglomerated acid (+-12S04) with a concentration of about 0.5 to 5%.
) was attached. Inside the duct, there were parts of the stainless steel material that were severely corroded, and the stainless steel material had to be replaced every year.

The resins, curing agents, etc. used in Table 1 are as shown below.

Epoxy polyacrylate resin (■) manufactured by Nigel Chemical Co., Ltd. [Resin obtained by reacting it with an equivalent amount of methacrylic acid using Epicor 1-828J. Viscosity 12400 voices (25°C).

Epoxy polyacrylate resin (■) manufactured by Nigel Chemical Co., Ltd. [Resin solid at temperature obtained by reacting Epikote 1001J with an equivalent amount of methacrylic acid.

Hisphenol type acrylate resin: 1-Hiscoat #700j manufactured by Osaka Organic Chemical Industry Co., Ltd., viscosity 1200 centibois (25°C).

Novolac-type acrylate-1-resin: A resin obtained by reacting an addition reaction product of 1 mol of 3,6-nuclear novolac resin with 5.0 mol of ethylene oxide and 3.6 mol of methacrylic acid.

Viscosity 7000 centipoise (25°C).

Curing agent (c): Tertiary butyl perbenzoate curing agent e: Methyl ethyl ketone peroxide: Tertiary butyl perbenzoate -1 to -6 (weight) Curing accelerator (P): 0% cobalt octylate curing accelerator 0: 0.2% vanadium octylate tertiary amine 0'1
Dimethyltoluidine Tertiary amine O dimethylaniline Also, Barcol hardness was measured using Barcol hardness tester type 934-1 specified in JISK-6911.

The rate of change in weight of the test piece was expressed as the rate of change with respect to the initial weight of the test piece.

As is clear from the physical property test results in Table 1, the FRP obtained by the present invention has a significantly high retention rate of initial physical properties even after 6 months and 12 months. On the other hand, in Comparative Examples 1 and 2 in which diallyl orthophthalate and diallyl isophthalate were used instead of diallyl terephthalate, the laminates had already undergone interfacial failure after 6 months. Furthermore, in Comparative Example 3, which contains a small amount of sialyl terephthalate, the retention rate of each physical property value after 6 months is less than 50%, and the weight change rate is also significantly higher than that of the present invention. Comparative example 4 with a large amount of sialyl terephthalate
However, the resin did not harden and physical property tests could not be performed. In addition, in Comparative Examples 5 and 6 where the resin component ratio is outside the range of the present invention, Comparative Example 5 has a small amount of epoxy polyacrylate resin.
'c has extremely low initial physical properties, and interfacial failure has already occurred after 6 months in the corrosion resistance test. In Comparative Example 6, which has a large amount of epoxy polyacrylate resin, the liquid viscosity is extremely high, so it is necessary to increase the amount of styrene. At the same time, the corrosion resistance is also significantly deteriorated.

Examples 7-8, Comparative Examples 7-8 Using the resin composition shown in Table 2 (each component of the composition is the same as in Table 1), the size was 130X in the same manner as in Examples 1-6. A test piece of 100x and h weight was prepared.

The above test piece was placed in the chlorine waste conduit of the alkali chloride electrolytic cell (=J), and the physical properties were measured after 6 months and 12 months in the same manner as in Examples 1 to 6, and the results are shown in Table 2. The test conditions were: chlorine scum temperature: 80-95°C; chlorine temperature: 95°C;
~100%, and the humidity was 100%.

As is clear from Table 2, in all the laminates of the present invention, the decrease in physical property retention was small and the weight change rate was also extremely small. On the other hand, in Comparative Example 7, in which diallyl orthophthalate was used instead of diallyl terephthalate, and Comparative Example 8, in which diallyl terephthalate had little darkness, both of them already softened after 6 months and the C Barcol hardness retention rate became zero. In addition, the retention rate of other physical properties also decreased significantly, and the weight change rate was also large.

Table 2 (Double weight part) Also, the same surface mat (S), chopped strand mat (M), and glass cloth tape (T) as in Examples 1 to 6 (rATG 25100X manufactured by Unitika Co., Ltd.
150-3AJ) and the composition of Example 8 as the resin, an FRP pipe (with an inner diameter of 125 mm and a thickness of 7 mm) containing a resin composition of 165% by weight consisting of a laminated structure of SM2TMTMTMMS was made in a wooden mold. Created. This was installed as part of the chlorine gas conduit in the electrolytic cell, and the wall thickness of the pipe was measured after one year of use. As a result, there was only a decrease of 0.5 to 0.8 TA, which was different from the conventionally used FRP pipe. (Using bisphenol type unsaturated polyester as the resin component) had 1.3 to 1.8 times the durability.

Examples 9-10, Comparative Examples 9-10 Glass fiber reinforcement similar to Examples 7-8 using a resin composition not shown in Table 3 (each component of the composition is the same as in Table 1) F with a resin composition content of 65% by weight in the base material and laminated structure
An RP pipe (inner diameter 75nφ, thickness 51.length 1+n) was produced. This was immersed in a 35% by weight hydrochloric acid solution (temperature 20 to 40°C) containing 0.1% by weight of benzene.
Physical properties were measured after 6 months and 12 months in the same manner as in Examples 1 to 6, and the results are shown in Table 3.

Looking at the physical property results in Table 3, Examples 9 and 10 both have a physical property retention rate of 90% or more after 12 months of immersion (), whereas Comparative Examples 9 and 10 have a physical property retention rate of 90% or more. The retention rate is only around 50% or less than 50%, and the weight change rate is also large.

Table 3 (Double combination section)
Further, using the resin composition of Example 9, a tank with an internal volume of about 10,711" (inner diameter 2,10"
0mm, height 3200. ) was created.

The glass fibers used were the same surface pine 1-(S) and chopped strand mat (S) as used in Examples 1 to 6.
M), and roving cloth (R) (manufactured by Nittobo Co., Ltd.
WR-570J), and the laminated structure is SM2R.
MRMRM2ST: Resin content was 60 to 70% by weight C.

A benzene-containing hydrochloric acid solution similar to that described above was placed in this tank, and the condition of the inner wall of the tank was observed after 1, 2, and 3 years, but no abnormality was observed.

Applicant: Osaka Soda Co., Ltd. Agent: Patent Attorney Toru Mayo

Claims (1)

[Scope of Claims] (a) Epoxy polyacrylate resin 50N80 4% by weight (b) Disphenol type or novolak type polyacrylate resin 50 to 20% by weight (a) and (b) above
The following (C) to (
(1>Component, (C) 20 to 80 parts by weight of diallyl terephthalate (d) 0 to 30 parts by weight of styrene (e
> 0.5 to 5 parts by weight of peroxide and/or alkyl peroxyester (f) 0.1 to 2 parts by weight of cobalt salt and/or vanadium salt (g) Tertiary Resin composition containing amines 0.01-0.1 parts by weight 20-
A method for producing glass fiber-reinforced plastics having excellent acid corrosion resistance at high temperatures, characterized by impregnating 90% by weight into 80 to 10% by weight of a glass fiber-reinforced base material and curing.