JPS58183719A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:The titled composition having reduced volatility of styrene monomer, obtained by blending a mixture of an unsaturated polyester and a bisdicyclopentadiene ester of an alpha,beta-unsaturated dibasic acid in a specific ratio respectively with a liquid polymerizable monomer. CONSTITUTION:100pts.wt. mixture of 25-95wt% unsaturated polyester and 5- 75wt% bisdichloropentadiene ester of an alpha,beta-unsaturated dibasic acid shown by the formula (X is 2-3C unsaturated hydrocarbon) is dissolved in 10-70pts.wt. liquid polymerizable monomer (e.g., styrene, etc.) to give a solution, to which an inhibitor (e.g., hydroquinone, etc.) is added, to give the desired composition. A polymerization initiator (e.g., benzoyl peroxide, etc.) and a promotor (e.g., cobalt naphthenate, etc.) are added to the composition, which is cured and molded. USE:A material for construction, transportation devices, industrial devices, electrical insulating material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an unsaturated polyester ll11 composition,
More specifically, it enables high solidity differentiation without impairing the inherent properties of unsaturated polyester resin, 4
The present invention relates to an unsaturated polyester resin composition that contributes to reducing the volatility of 1HC styrene and to water-resistant china clay.

The unsaturated polyester resin is usually made of a polyhydric alcohol component mainly composed of glycols, an α,β-unsaturated dibasic acid or its anhydride, and a polybasic acid in which a saturated dibasic acid or its anhydride is further added if desired. The components are reacted to obtain an unsaturated polyester, which is used in the form of a liquid polymerizable monomer for crosslinking, mainly a styrene monomer. This resin has characteristics such as being easier to mold than other curable resins and being able to exhibit a variety of excellent storage and chemical properties by selecting the main raw materials. Its characteristics are utilized in many applications such as corrugated sheets in the field of reinforced plastics, reef construction materials such as 1I-1 septic tanks; ships,
It is used for six types of transportation equipment such as O fist cars; tanks, containers, pipes, and industrial equipment such as corrosion-resistant equipment.In the field of non-reinforced plastics, it is used for electrical insulation materials, cashier 7 mortar, resin concrete, decorative boards, gel foot, It is used for various purposes such as putty and Ik material. However, the molding methods applied to these applications today are
In the summer season, the volatilization of styrene monomer, which is mainly used as a one-liquid polymerizable monomer, is one of the causes of the deterioration of the agricultural environment due to the use of hydrogen hydride systems.

As a method to improve the deterioration of the working environment, (1) use a monomer having lower volatility than styrene monomer as a liquid polymerizable monomer.

(bl) Lower the molecular weight of unsaturated polyester to reduce the proportion of styrene monomer in the unsaturated polyester resin.

tc) Adding a substance that suppresses the volatilization of styrene.

etc. are possible. However, in method (a), the low volatility monomer is compared to styrene.

High viscosity leads to high viscosity t of unsaturated polyester resin (1), which makes workability
It has disadvantages such as being more expensive than non-electronics. (In the - method, the lowering of the molecular weight of unsaturated polyester is
It is difficult to avoid the inconvenience of causing a severe decrease in the performance of the tr.

(In the cl method, no substance other than wax has been found to effectively suppress the volatilization of methylene (Tsuma), and the addition of wax may have a negative effect on secondary adhesion depending on the curing conditions. Therefore, it cannot be an appropriate means of deciding wIJ.

In view of this situation, Akishita Kimi et al. reduced the proportion of styrene monomer, which is a liquid polymerizable monomer, in unsaturated polyester 11111, thereby greatly reducing the amount of flaccidity. Moreover, 1 liter of unsaturated polyester
The present invention was developed as a result of extensive research to obtain a tree Mt in which the inherent characteristics of IN are not impaired in any way.

That is, 1 the present invention provides (1) unsaturated polyester 25-
95% by weight, and a biscyclopentadiene ester of an α,β-unsaturated dibasic acid represented by the general formula (bl (in the formula, X represents an unsaturated hydrocarbon group having 2 or 3 carbon atoms)) 5 - Mixture 1 consisting of 51% by weight of
An unsaturated polyester resin composition comprising 10 to 70 parts by weight of a liquid polymerizable monomer based on 01001t, the polymerizable monomer of the casing, specifically styrene
It has now been discovered that, despite the significant reduction in the amount of volatilization of the unsaturated polyester IlIM, the original properties of the unsaturated polyester IlIM are not only sufficiently maintained, but also the water resistance of the cured resin is improved.

, composition E! of the invention! The general formula used in
The bisdicitalobentadiene ester of an α,β-unsaturated dibasic acid is represented by:

For example, dicyclobentadiene/tannin or humanoxylated dicyclobentadiene/(trizicouve(5°1.1.0”°6
]-5-dese7-8 (t or 9)-all) and mkyo”
Alpha such as lemon ash, male ash, 7-ful acid, itaconic acid, etc.
,-! - An esterification or addition reaction can be carried out with an uncooked electrolyte base 1llI or its anhydride in a manner known per se, without using tIks or, if necessary, with a known Lewis acid or the like. Ghostly.

The unsaturated polyester used in the composition of the present invention refers to known ones, such as a polyhydric alcohol component and an unsaturated polybasic acid or anhydride thereof.

Ordinary unsaturated polyester obtained by reacting an electrolyte polysalt device or its anhydride as necessary; polyhydric alcohol component and electrolyte polybasic acid or its monohydrate; unsaturated polybasic as required for HIE Polyester (meth)acrylate obtained by reacting terminal k(meth)acrylic acid of polyester obtained by reacting with acid or its anhydride, dalicidyl (meth) 7-ester, etc.; The polyhydric alcohol component used here includes ethylene glycol, diethylene glycol, buOhiL/noglyfur, and dibuvirendaricol.

1.3-butanediol, 1.4-butanediol, 1
．． 6-hexane diol, neopentyl glycol, trimethy4-propane, pentaerythritol, 1.1
'-imbupylidene-bis(p-phenyleneoxy)
-di-bupanol-2,1,1'-imbupylidene-bis(p-phenylene-oxyno-di-ethanol-
I can list 2 and so on. Examples of unsaturated polybasic acids or anhydrides thereof include maleic anhydride, maleic acid, 7-malic acid, itaconic acid, citraconic acid, etc., and examples of saturated polybasic acids or anhydrides thereof include phthalic acid, phthalic anhydride, Examples include isophthalic acid, prephthalic acid, succinic acid, adipic acid, trimellitic acid, and trimellitic anhydride.

The liquid polymerizable monomer used in the composition of the present invention includes:
Styrene, α-methylstyrene, rinnostyrene7. p-
Vinyl aromatic compounds exemplified by t-butylstyrene, vinyltoluene, divinylbenzene; Allyl compounds exemplified by diallyl cyanurate; methyl acdarate, methyl methacrylate, glycidyl methacrylate, etc. Examples include acrylic compounds exemplified by. The polymerizable monomers of these casings are
Alternatively, they can meet by appropriately using two or more types together.

The inhibitor used is when unsaturated polynisdel is dissolved in a predetermined housing of polymerizable monomers.

Known compounds such as hydroquinone, p-t-butylcatechol, 7-not-t-butylhydride p-quinone, toluhydroquinone, and hydroquinone monomethyl ether can be used.

When curing the unsaturated polyester resin composition of the present invention, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl hexaton peroxide, a-hexyl nonperoxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, - The polymerization initiator used in ordinary unsaturated polyester resins, exemplified by t-butyl peroxide, is used, and the accelerator is also commonly used in unsaturated polyester resins. .

Cobalt otatenate, aliphatic amine, aromatic amine, acetylacetone, 7cetoacetic acid ethyl ester *tIJl
Alternatively, a mixture of two or more types may be used.

In the composition of the present invention, the weight ratio of the unsaturated polyester as the dark component to the bis-dicyclobentadiene ester of α,β-unkojiwa dielectric acid as the component (b) is (a)/(
bl = 25-9575-75.

(b) When the proportion of the component is lower than 5% by weight, the working viscosity increases, so the amount of liquid polymerizable monomer must be increased, and therefore, low volatility of this monomer cannot be achieved. At the same time, the water resistance of the cured product will not be improved. On the other hand, if the proportion of component tb) exceeds 75% by weight, the high temperature curability of the yield-like unsaturated polyester resin will be affected due to the lack of crosslinking points, and the water resistance of the cured product will not be improved. This leads to deterioration of workability and deterioration of the physical properties of the cured product.

I compound of (1) component and (-) component 100 weight 11?
! The polymerizable monomer for the housing must be blended in an amount of 10 to 70 parts by weight. The content of this monomer is 10
If it is less than 1 part by weight, the viscosity of the *-like unsaturated polynisder resin becomes high (1, deterioration of workability Vtll1<, and the cured product 11 decreases at the same time), m side, and the content of this monomer is 70%. If the amount exceeds the amount by weight, the object of the present invention, which is to reduce the volatility of the monomer in the unsaturated polyester l1liICJi, cannot be achieved.

In the composition of the present invention, α is component (b).

The presence of the bisdisicupentadiene ester of the β-unionized dibasic acid has a very redundant meaning. By blending the polyester bisester, the content of liquid polymerizable monomers, such as styrene monomers, can be reduced without impairing the workability of unsaturated polyester resins, and as a result, the monomer content can be reduced. At the same time, it is possible to maintain the original mechanical properties of the unsaturated polyester lI41I cured product and improve its water resistance. The reason why the mechanical properties of the cured product obtained from the composition of the present invention are comparable to those of commercially available cured unsaturated polyester resins despite the low content of liquid polymerizable monomers is that Although the details are not clear, it is thought that copolymerization of the polymerizable monomer of the casing and bisdicyclopentanene ester of α,β-unsaturated dibasic acid contributes. Furthermore, the reason why the water resistance of the cured product improves is that both ester groups of this bisester and the ester groups in the unsaturated polyester containing the at acid component are sterically held by the dicyclopentadiene ring. It is presumed that the reason for this is that the hydrolysis of the reservoir ζ is inhibited.

Various additives or fillers may be added to the unsaturated polyester resin composition of the present invention as desired, and fiber reinforcing materials may also be used.

Depending on the quantity, it may be used in a desired shape such as 8MC or BMC.

Next, the unsaturated polyester tree composition V of the present invention will be specifically explained using Examples and Comparative Examples.

Reference Example [Synthesis of unsaturated polyester] Synthesis 111 Phthalic anhydride 142?
i Maleic anhydride 10791 and boupylene glycol 1841g were charged and reacted at 215°C for about 6 hours to obtain unsaturated polyester (a) with an acid value of 24.8.

Synthesis Example 2 Into the same apparatus as in Synthesis Example 1, 18271 inphthalic acid and 1841 g of propylene glycol were charged, and 180 g of propylene glycol was charged.
After reacting at ~210°C until the acid value reached 9, the warped product was cooled to 150°C, and maleic anhydride was added to it.
07? The mixture was charged with JF and then reacted at 220°C for 10 hours to obtain an unsaturated polyester (b) with an acid value of 1B and 0.

Synthesis Example 3 Terephthal 511B271.
゛Propylene glycol 1 @411 and an organic tin compound as a catalyst are charged, and the acid value is 1 at 180-215℃.
The reaction product of Example 1 was cooled to 150°C, and Km water maleic $ 1079N was added thereto. Then, the reaction product was reacted at 210°C for 12 hours to obtain an unsaturated polyester f1 with an acid value of 14.5. Ta.

Synthesis Example 4 Into the same apparatus as in Synthesis Example 1, unsaturated polyester (b) 28001 styrene monomer obtained in Synthesis Example 2 was added.
200 jl and 0.8 g of hydroquinone were charged, and the unsaturated polyester was dissolved in the styrene monomer. Dalicidyl methacrylate 1791 and a basic catalyst were added to this *** and reacted at 120°C for 5 hours, resulting in an acid value of 0°7.
Dalicin lumetasylate-modified unsaturated polynisderensis) was obtained.

Reference Example B [Acid-containing bisdicyclopentanene ester] Hydroxytriated dicyclopentadiene 5605N and maleic anhydride 11771 were charged in the same apparatus as in Synthesis Example 1, reacted at 120°C for 5 hours, and then heated. then 2
The reaction was carried out at 05° C. for 4 hours to obtain a pale yellow tassel box. This was a warm mixture of bisdisic a pentadiene 7 malate and bis dicitape 7Jp die/maleage.

Hereinafter, this will be referred to as "bisester".

Example 1 □ Unsaturated polyester (A) obtained in Synthesis Example 1 15
75g and bisester 525y obtained by synthesis AS to make styrene senomer? 00jF[ill was solved to obtain unsaturated polynisdel*m(4). This<? -Jyuju- Add tilcatechol and have a predetermined room temperature gelling time (20℃)@! IIEf14*shita.

Example 2 Unsaturated polyester (A) obtained in Synthesis Example 1 1゜13y
By combining the bisester 125ai obtained in Synthesis Example 5 and t-styrene 750IC*, an unsaturated polyester resin (6) was obtained. To this, pt-butylcatechol was added, and a tree 1i [-
I glanced at it.

Example 3 Unsaturated polyester intermediate 1 obtained in Synthesis 1i12 1050
g and bisester 105011 obtained in Synthesis Example 5 were dissolved in 900 g of styrene senomer to obtain an unsaturated polyester resin. P-t-butylcatechol was added to this to adjust the resin to have a predetermined room temperature gelling time (20 tl).

Implementation f14 Unsaturated polyester xIP) 876y obtained in synthesis f42 and bisester 1514I obtained in synthesis example 5 were dissolved in styrene (Zuma-8101), and unsaturated polyester 41
1111 ([) was obtained. To this, ρ-1-butylcadecol was added to adjust the resin to have a predetermined permanent gelation time (at 20° C.).

Example 5 Unsaturated polyester obtained in Synthesis Example 5? 112871 and 693 g of the bisester obtained in Synthesis Example 5 were dissolved in styrene (Zuma-10211) to form an unsaturated polyester base l1.
I got i1@. p-1-butylcatechol was added to this to adjust the resin to have a predetermined room temperature gelling time (20°C).

Example 6 The glycidyl methacrylate-F modified unsaturated polyester resin obtained in Synthesis Example 4) was combined with 1492N and the bisester 804N obtained in Synthesis@5 with t''f1, and then styrene (
An unsaturated polyester crosslinker η was obtained. This and cp-t-butylcatechol were added to adjust the resin to have a predetermined normal temperature gelling time (20° C.).

Comparative Example 1 Unsaturated polyester obtained in Synthesis Example 1) 185011v
Styrene 7-mer-1170jlK was dissolved and unsaturated polyester resin M(m)V was soaked. In addition to Kp-t-butylcatechol, I
Adjusted to ltM.

Comparative Example 2 Unsaturated polyester obtained in Synthesis Example 2 (→ 1590.9
The unsaturated polyester resin (b) was obtained by dissolving the resin in V-styrene Nanatsumar-1410II. By adding kp-t-butylcatechol, the resin was adjusted to have a predetermined normal temperature gelling time (20°C).

Comparative Example 5 Unsaturated polyester (c) obtained in Synthesis Example S 15901
11kX+ and 74/-1-1410jl#c@ were solved to obtain an unsaturated boester resin. Add pl-butyl catheter to this and gelatinize at room temperature for a predetermined time <20 tl:)
Adjusted to a resin with I.

Comparison N4 2250jK styrene monomer 7701v and unsaturated polyester It lit
(d) was obtained. 1p-1-Butylcatechol was added to this resin j (II
IIL, ta.

Example 7 *The characteristics of the various unsaturated polyester resins obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were determined.

Unsaturated polyester tree III ~ (to) and (1) ~ (
The viscosity of the resins shown in Tables 1 and d), whose liquid properties are shown in d), was adjusted to about 6007 inch bores at 25°C. Room-temperature gelation time was determined by adding 6% cobalt heptathenate solution to each resin held at 20°C, 0, 5 phr, and 55 phr.
% Methyl Ethyl Chthone Peroxide #I Moat 1-Op
Add kr and warm, JI8 K 6901-1
It was measured according to the standard in Section 4.8 of 977. The amount of styrene monomer volatilization is at a temperature of 20°C and a relative humidity of 55-60%.
The measurement was carried out in a thermostatic chamber maintained at a temperature of approximately g-1 sm/sec.

The measurement method is as follows.

On the lid of a round can with an inner diameter of 66Ils1 and a surface area of 34.2d,
6% naphthi/acid cobalt 1% [0,5 pbr and 55%
Methyl ethyl ketone peroxy)-11111, Oph
Pour 5.41 lIN mixed with r into 45 (1,?/I
The relationship between time and the amount of styrene monomer volatilization was determined by placing 11 plies of styrene monomer chopped strands on top of it.After about 100 minutes, almost no styrene monomer volatilization was observed. The value is expressed by converting the amount of styrene chloride volatilization after 120 minutes into I/m''K. 1m! As is clear from the results of 1, the unsaturated polyester resins (4) to (g), which were subjected to KIIIE, have significantly lower styrene content than those of (a) to @). It showed the volatility of zuma.

Table 2 shows the characteristics of each 111iI footplate.

The casting plate contains 6% cobalt naphthenate 11 moat 0 for each resin,
5 pkr and 1.0 pbr of 55% methyl ethyl ketone peroxide solution tIL were added and mixed, left at 20°C for 16 hours, and then cured at 100°C for 2 hours. A product with a thickness of 3 sheets was used. . - The bending strength and flexural modulus are as per 5.2 of J■8K t5919-1976.
The boiling water absorption rate in Section 11 was determined in accordance with the provisions of Section 5 and 2.7. The color strength and self-elastic modulus of the unsaturated polyester IIIN are the same as those of the corresponding (a>~(di). It can be seen that significant improvements have been achieved in terms of retention of self-strength and self-elastic modulus after immersion in boiling water.

□Have a drink

Claims (1)

[Claims] α represented by t (al unsaturated polyester 25 to 95% by weight and (bl general formula % formula % (wherein, X represents a carbon a2t or S unsaturated hydrocarbon group) , bisdicyclopentadiene ester of β-unsaturated dibasic acid 5 to 5% by weight. Polyesdell resin composition