DE2252931C3 - Partially cured molding compounds, process for their production and their use for the production of moldings - Google Patents

Description

has been obtained, heated to temperatures of 80 to 160 ⁰ C for so long that it does not harden completely and can cool while being shaped into a non-sticky, solid-like, suitably shaped, ^{hardenable at 120 to 180 0 C mass.}

3. Use of the molding composition according to claim 1 for producing hardened moldings.

Mixtures which contain an unsaturated polyester and η polymerizable monomer, such as styrene or an acrylic acid ester, are known. To produce moldings, these mixtures can be mixed with pigments and fillers as well as fibrous strengthening agents and hardened with heating. The curing reaction can also be carried out at room temperature using a polymerization initiator together with a polymerization accelerator which activates the polymerization initiator. According to this process, solid shaped pieces are obtained from the mixtures mentioned. Mixtures of this type, however, have the disadvantage that they are liquid at room temperature, that their handling is inconvenient and that it is difficult to continuously produce molded pieces from them.
To avoid these disadvantages, processes have recently been proposed in which solid-like compositions are formed by modifying liquid, thermosetting synthetic resins or synthetic resin compositions.

ίο In the field of unsaturated polyester, it is known either to use a polymerizable monomer that is solid at room temperature, or by adding a metal oxide such as MgO or a metal hydroxide such as Ca (OH) ₂ to a solution of an unsaturated polyester in Styrene is a dry premix for resin mats or for pourable or pourable molding compounds. Fittings made from these molding compounds have the following disadvantages:

(1) Stress occurs due to severe shrinkage during curing;

(2) the hardness and consequently also the brittleness is considerable;

(3) the fittings are highly flammable;

(4) yellowing or degradation occurs under UV irradiation;

(5) the voids have poor durability against alkalis or boiling water, as the ester bonds are easily split hydrolytically will;

(6) Due to the exothermic reaction, the fitting cracks and warps slightly thickly Put;

(7) Processing is difficult because of the short pot life of the molding compounds.

In a known method for the simple production of molded parts from vinyl chloride polymer molding compounds becomes a non-reactive plasticizer for a vinyl chloride polymer powder for pastes Formation of a Polyvinylchloridplastiso'ls incorporated, the sol melted by heating and under conversion processed into a gel to form a molded piece (see. US-PS 29 43 952 and 30 66 110 and GB-PS 6 94 444). Moldings made from such polyvinyl chloride plastisols, however, have the following Hot off:

(1) The molding has a low hardness and a low dimensional stability;

(2) the oil and solvent resistance of the molded piece is low;

(3) the stain resistance of the molding is poor;

(4) Materials that are in contact with the fitting are removed by migration of the soft

machers attacked.

To eliminate these disadvantages, molding compositions have been developed which contain a vinyl chloride polymer and a reactive plasticizer or a vinyl chloride polymer, contain a monomeric vinyl compound and a non-reactive plasticizer (see. US-PS 28 49 332, 29 18 736, 31 33 825, 35 57 046 and 35 57 049). However, the chemical resistance, hardness and dimensional stability of these molding compounds in which heat and other properties are not sufficiently achieved.

In addition, these molding compounds are liquid at room temperature. Their handling is troublesome, and so are they

T ⁴

.j difficult to automatically deform under (B) 20 to 70 percent by weight of a monomeric

! / [! using SMC. Vinyl compound,

To overcome these disadvantages, (C) 10 to 65 percent by weight of a vinyl chloride

·, Process developed in which a vinyl polymer and

fluoride polymer and a reactive plasticizer, 5 (D) 0.2 to 3 percent by weight of a polymerization oil Diacrylic acid glycol ester, containing; v4asse on initiator containing mass. = Temperatures from 90 to 120 ° C is heated. Here

«The vinyl chloride resin with the plasticizer is grooved so long to temperatures of 80

! «He formation of a gel. The resulting gel is heated to 160 ° C, so that it is not yet completely

If temperatures of 120 to 200 ° C result in hardening. When cooling while shaping

* Γ the cured fitting is heated (see US-FS a non-sticky, solid-like, partially

35 57 046). ^{get hardened mass} . This mass lets itself through

Also a vinyl chloride polymer and completely unheated to temperatures of 120 to 180 ° C

“As a reactive plasticizer, polyester should harden.

Holding mixtures are known (see. US-PS 31 33 825 15 As unsaturated polyester is preferably a

ud 33 ⁶ 3 ° ^{28 and ÜB} " ^{PS 7 65 562} > · ^These mixtures used polycondensate, the from (a) 1 g equivalent

However, due to the poor compatibility of an unsaturated dicarboxylic acid or a mixture thereof

For both polymers, an unsatisfactory bearing with a saturated aliphatic or aromatic one

Accordingly, only a very small amount of an-dicarboxylic acid and (b) 1 to 1.2 g-equivalent of one

! of your unsaturated polyester a vinyl chloride polyhydric alcohol, namely neopentyl glycol

S merisat incorporated. or 1,6-hexanediol, alone or a mixture of

In addition, the mass obtained is generally at least 0.2 molar equivalents of neopentyl glycol and

«Very viscous and the viscosity increases because of the 1,6-hexanediol or these alcohols with a

The unsaturated polyester is not compatible with other glycols

the vinyl chloride polymer in the mixture of the monomeric vinyl compound (B) is preferred

Sen polymers abruptly and gelation occurs wise styrene or a mixture of styrene with emer

Furthermore, it is very difficult to create molding or other Vu

Bcschichtunesssteps to carry out since the mass is used.

Pine has a very short pot life. It is also used as a vinyl chloride polymer (C)

such a mixture obtained 30 a vinyl chloride polymer powder, which for

. . . , ,,. ,. t -υ: * :,. ♦ _m ; t »irKMTi Hurchschni

^P Del invention is based on the object, partially average particle size of 0.05 to 50 μΐη ver cured molding materials on the basis of a loosely turns. "," Ricatinminitiator ver

cut, bent and processed. of decay

In addition, a method of making this embodiment is intended to be a liquid one

^ £ ^ S ^^^? ^ £ Ä TrÄ & stir and mix

for the production of fittings with an excellent 45 one

Hardness pliability, impact resistance, abrasion _(A ' _} 5 to 70 percent by weight of an unsaturated strength chemical resistance, heat resistance polyester with an average condensation

and fire resistance. These tasks are graded at least 4 and a ^ men-

Sen solved by the invention, mean molecular weight of at least

The invention thus relates to what is defined in claims _50-1000

marked ^ object. (B ') 20 to 70 percent by weight of a reactive We.ch-

From DT-OS 21 21 225, molding compounds or a mixture thereof with a mono

knows that an unsaturated polyester resin, a vinyl _meren vinyl compound, vinyl chloride

chloride polymer, a reactive plasticizer and _{(C) 10 to} 65 percent by weight of a vinyl chloride containing a polymerization initiator. The inven- 55 polymers and. Commercialization

Partially cured molding compositions according to the invention are characterized by _(D ' _} 0.2 to 3 percent by weight of a polymerisation material which are characterized by substantial improvements

In the following, the invention is based on two ^ _{long on temperatures} of

Embodiments explained. . «I60 ° C warmed that not yet complete

In the first embodiment, a liquid 60 80 to 60 C warmed _{shape is used}

Mixture, which by thorough stirring and mixing ^ jj ^ t ffiwU solid-like, partially formed

a _hardened mass obtained. This mass lets itself through

(A) 5 to 70 weight percent of unsaturated heating to temperatures of 120 b.s.

^(A) polyester having a condensation durchschnitjichen 6 ₅ '^^ _Ausfühmngsf orm, the same

degree of at least 4 and a numerical Be ^the ^^ ^e " _{(A) d} ^ _s equal vinyl chloride

average molecular weight of at least unsaturated pol yen KJ, ^ pimerisat.ons

initiator as used in the first embodiment, viscosity and good shelf life is preferred will. an unsaturated polyester used, which by

Examples of the monomeric vinyl condensation used of (a) 1 molar equivalent of one of the prebond (B ') are styrene and its mixtures with said unsaturated dicarboxylic acids or one other monomeric vinyl compounds. 5 Mixture of one of these carboxylic acids with one of the

Reactive plasticizers (B ') can be, for example, aliphatic or aromatic dicarbons Compounds of the general formula acids with (b) 1 to 1.2 molar equivalents of neopentyl

glycol or 1,6-hexanediol alone or a mixture of at least 0.2 molar equivalent, in particular ίο 0.3 molar equivalent, neopentyl glycol, 1,6-hexanedioI or both alcohols with another polyhydric Alcohol has been made.

CH ₂ = CCO- -A- -0-CC = CH ₂

This unsaturated polyester prevents the on

increase in viscosity in the used as starting material, in which A the remainder of a compound 15 turned liquid mixture and sedimentation with at least two terminal hydroxyl groups, or precipitation of vinyl chloride polymer particles. which optionally contains at least one ester or ether. Therefore, the pot life of the liquid bond used can contain, and X means a hydrogen or halogen mixture by using this unsaturated atom, a methyl or ethyl group and polyester can be extended. μ and m have the value 1, 2 or 3. * o Preferably the unsaturated polyester has one

F i g. 1 shows the by thermal differential average degree of condensation from minanalysis of the product of the invention obtained at least 4 and a number average molecular weight thalpie curve for the corresponding temperature curve of at least 1000. Are unsaturated poly-

F i g. 2 shows the differential thermal esters with a degree of condensation of less than 4 Analysis of the product of the invention and that used according to «5 is the partially cured molding compound the product obtained in the comparative example obtained sticky, and the mechanical properties of the full enthalpy curve for the corresponding temperature-permanently cured fittings are bad. There Curve. the unsaturated poly-

F i g. 3 shows that thermal differential esters reduce the stickiness of the partially cured form analysis of conventional molding compounds, it is possible to use a large number of pie curves for the corresponding temperature curves of vinyl monomers and the strength (the enthalpy curve is for better explanation C of the partially cured molding compound. From FIG. 2 also reproduced in FIG. 3). for this reason, the partially hardened mold

In the production of molding compounds according to DT-OS, compound without reinforcement material, such as glass fibers, ver-21 21 225 is the use of a reactive soft 35 turn.

machers indispensable. In the inventive method, the unsaturated polyester is used in an amount of

A reactive plasticizer is not necessarily 5 to 70 percent by weight used. If you need hold less than 5 percent by weight

In the process according to the invention, the usual aforementioned improvements cannot be achieved, and at unsaturated polyester, which increases to the production of 40 a content of more than 70 percent by weight Castings, decorative panels, laminates and the viscosity of the liquid originally used Paints suitable, can be used. The un- mixed, so that it is practically worthless, Saturated polyesters are formed by condensation of As a vinyl chloride polymer, a homopoly-

unsaturated polybasic carboxylic acids with a plurality of vinyl chloride or a copolymer of high-quality alcohols produced. Most unsaturated vinyl chloride with other copolymerizable monomers Polyesters contain proportionally saturated several are used. For example, this can basic carboxylic acids or aromatic polybasic vinyl chloride with vinyl acetate, vinyl propionate, methyl carboxylic acids condensed. methacrylate, butyl acrylate, vinylidene chloride, acrylic

Examples of unsaturated polybasic carbonitrile, vinyl ethers, diethyl maleate, acrylic acid, methic acids or their derivatives are maleic anhydride, acrylic acid or maleic anhydride copolymerized Fumaric acid and itaconic acid. Examples of being saturated. In addition, saponification products can be a polybasic carboxylic acids or their derivatives are copolymers of vinyl chloride and vinyl acetate ver-phthalic anhydride, Isophthalic acid, tetrahydro- are used.

phthalic anhydride, adipic acid, tetrachloro For the production of shaped pieces or foils with

phthalic anhydride, hexachloro - endomethylene 55 excellent physical properties it is tetrahydrophthalic acid, terephthalic acid, sebacin- important that the homopolymer or copolymer acid, 3,6 - endomethylenetetrahydrophthalic acid an- of vinyl chloride a high degree of polymerization hydride, methylbicyclo - [2.2.1] - heptene - 2,3 - dicar-. In general, the use of a acid, tetrabromophthalic anhydride, TrimeUit homopolymers or copolymers of vinylic anhydride, Pyromellitic anhydride and hexa- 60 chloride with a degree of polymerization of 500 to chlorocyclopentadiene - tetrahydrophthalic anhydride. 2500 preferred Preferred particle sizes of the vinyl

Examples of polyhydric alcohols are ethylene chioridpolymerisats are 0.05 to 50 μπι, while glycol, propylene glycol, diethylene glycol, dipropylene particle sizes of 0.2 to 2 μm are particularly preferred GlykoL hydrogenated bisphenol, 1,5-PentanedioI, 1,3-Bu- are. The best results will be when using tanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 65 of vinyl chloride homopolymers or vinyl chloride-2,2'-di - (4 - hydroxypropoxyphenyl) - propane, neovinylacetate copolymers with a vinylchloidpentylglycol and dibromoneopentyl glycol. content of 95 to 99 percent by weight obtained that too

Can be processed for the production of liquid molding compounds with a lower plastisol. To the her-

It is possible to produce plastisols with a low viscosity, and coarse-grain vinyl chloride polymers as extenders with a particle size of 5 to 100 μ, ίτι to be used together with the homopolymers or copolymers mentioned.

The vinyl chloride polymer used according to the invention adsorbs the vinyl monomer, the reactive plasticizer and the unsaturated polyester. Included the viscosity of the mixture increases and the rate of polymerization can be controlled, whereby the physical properties of the fully hardened mass are not impaired.

The vinyl chloride polymer content of the starting mixture is 10 to 65 percent by weight. With a vinyl chloride polymer content of less than 10 percent by weight the aforementioned effects cannot be achieved; at a vinyl chloride polymer content of more than 65 percent by weight, the viscosity of the liquid starting mixture increases, see above that it no longer has any practical value.

Monomers which have a double bond in the molecule can be used as the monomeric vinyl compound contain. Examples of these monomers are styrene, chlorostyrene, tert-butylstyrene, vinyltoluene, divine) benzene, vinyl acetate, methacrylic acid esters, such as ethyl, butyl, 3-methoxybutyl, cyclohexyl, n-octyl, 2-ethylhexyl, lauryl and glycidyl methacrylic acid esters, and acrylic acid esters such as methyl, ethyl, butyl, 3-methoxybutyl, cyclohexyl, n-octyl, 2-ethylhexyl, Lauryl and glycidyl acrylic acid esters.

The vinyl compound is added to the liquid starting mixture to adjust the viscosity of the mixture and to improve the chemical resistance and mechanical properties of the molded article obtained incorporated.

The unsaturated polyester dissolves in the monomeric vinyl compound. This makes dispersion easier of the vinyl chloride polymer powder. Besides that it copolymerizes with the unsaturated polyester or the reactive plasticizer and improves the physical properties of the fully cured product. The monomeric vinyl compound is generally adsorbed on the vinyl chloride polymer. That is why it possesses the full Curing reaction has a high reactivity, with a strong heat of polymerization being developed. This has the consequence that the final hardening of the molding compound at relatively low temperatures, i. H. in the range from 120 to 180'C, can be carried out.

Of the aforementioned monomeric vinyl compounds, styrene is particularly preferred.

If component (B) of the mixture used according to the invention consists of only one monomeric Vinyl compound, it is added in an amount of 20 to 70 percent by weight. At a Content of less than 20 percent by weight, the viscosity of the liquid starting mixture is too high, and at a content of more than 70 percent by weight, the reactivity is so high that with partial curing Difficulties arise and the fully cured product is brittle and therefore worthless. Out For the same reasons, that of a monomeric vinyl compound and a reactive plasticizer is said to be existing component (B ') make up 20 to 70 percent by weight of the mixture.

If styrene is used alone as the monomeric vinyl compound, its content is also 20 to 70 percent by weight. When using a mixture of styrene with another monomer Vinyl compound, the mixture preferably contains 20 to 95 percent by weight styrene and 5 to 80 percent by weight the other vinyl compound.

The reactive plasticizer added to the liquid starting mixture is an acrylic acid ester of the general type formula

CH ₂ = CCO

Il ο

AfO-CC = CH ₂

in which A denotes the remainder of a compound with at least two terminal hydroxyl groups, which optionally contains at least one ester or ether bond, and X denotes a hydrogen or halogen atom or an alkyl group, such as the methyl or ethyl group, and / i and m denotes the value Have 1, 2 or 3.

Examples of reactive plasticizers are ethylene glycol dimethacrylate, Propylene glycol dimethacrylate, 1,3 - butanediol dimethacrylate, 1,4 - butanediol dimethacrylate, 2,3 - butanediol dimethacrylate, 2 - ethyl-1,3 - hexanediol dimethacrylate, 1,5 - pentanediol dimethacrylate, 1,6 - hexanediol dimethacrylate, neopentyl glycol dimethacrylate, glycerol trimethacrylate, dimethacrylate! - (bis - diethylene glycol) - phthalate, dimethacrylic (bis - diethylene glycol) maleate, tetramethacrylic - (bisglycerin) - phthalate, triethylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. In addition, reactive plasticizers of the AHyI type can be used, such as allyl acrylate, triallyl cyanurate, diallyl maleate, diallyl itaconate, diallylsebacate, Diallyl adipate, diallyl glycolate, triallylaconitate, diallyl monooclyl phosphate, Triallyl phosphate, diallyl isophthalate and diallyl benzene phosphate.

Furthermore, as reactive plasticizers, alkyl esters of Λ, / 3-unsaturated carboxylic acids, in which the Alkyl radicals preferably have 4 to 16 carbon atoms, such as maleic acid dibutyl ester, Maleic acid dicyclohexyl ester, maleic acid dioctyl ester, fumaric acid dibutyl ester, fumaric acid dicyclohexyl ester, Fumaric acid dioctyl ester, itaconic acid dibutyl ester, itaconic acid dioctyl ester, acrylic acid cyclohexyl ester, Acrylic acid octyl ester, acrylic acid lauryl ester, Cyclohexyl methacrylate, octyl methacrylate and lauryl methacrylate.

Either one reactive softener alone or mixtures of two or more of these softeners can be used Makers are used.

According to the invention it was found that di < reactive plasticizer, the compatibility between the vinyl chloride polymer and the unsaturated polymer Polyester increase and the mechanical properties the dimensional stability in the heat and the transparency of the fully cured fittings ver improve.

With regard to the curing speed the use of reactive plasticizers of acrylic acid ester type is not preferred because they are under de aforementioned reactive plasticizers have the highest curing speeds.

The reactive plasticizers can m

22 52 93 ϊ

of the monomeric vinyl compound can be used. The one combined with a monomeric vinyl compound reactive plasticizers dissolve the unsaturated polyester or disperse the vinyl chloride polymer forming a plastisol. After the reactive plasticizer has been added, this has according to the invention liquid mixture used has a low viscosity. Due to the small changes in viscosity the workability of the mixture is greatly increased.

When using a reactive plasticizer alone its content is 20 to 70 percent by weight and when using a reactive one Plasticizer and a monomeric vinyl compound is the total amount of the two ingredients 20 to 70 percent by weight. The mixing ratio of the reactive plasticizer is preferably to monomeric vinyl compound 1C0: 0 to 5:95.

The amount of the polymerization initiator in the liquid starting mixture is 0.2 to 3 percent by weight. Organic peroxides with a high decomposition temperature at which the 1 minute half-life of the decomposition (// Z) is above IfO ¹ C are preferably used as polymerization initiators. Examples of such initiators are methyl ethyl ketone (HZ = MYC), cyclohexane peroxide (HZ = - 174 ' C), tert-butyl hydroperoxide (HZ = 179X), p- (m) menthane hydroperoxide (HZ = 216'C) cumene hydroperoxide (// Z = 255'C), 2,5-dimethylhexane-2,5-dihydroperoxide (HZ = 257'C), tert-butyrperbenzoate (HZ = 170X), tert-butyl peracetate (HZ = IfOX), di-tert-butyl peroxide (hZ = 186X). Dicumyl peroxide (// Z = 171X), 2,5-dimethyl-2,5-di (tert-butylperoxyVhexane (HZ - 179X), 2,5-dimethylhexane-2,5-di- (hydroperoxide) (HZ = 257 'C), diisopropylbenzene hydroperoxide (HZ = 2O5X) and di-tert-butyl perphthalate (HZ = 159 C) These polymerization initiators can be used alone or as a mixture of at least two of these compounds.

It is also possible to use mixtures of the aforementioned organic peroxides with polymerization initiators, the corresponding decomposition temperature of which is at most 150.degree. Examples of these initiators are benzoyl peroxide (HZ = 130X), p-chlorobenzoyl peroxide (HZ = 137x), 2,4-dichlorobenzoyl peroxide (HZ = 121X), propionyl (HZ = 118X), lauroyl peroxide (HZ = 114X). Acetyl peroxide (HZ = 123X), tert-butyl peroxyisobutylate (HZ = 133X), succinic acid peroxide (HZ = ~ - 131X), diisopropyl peroxyüicarbonat (HZ - 88X) and <x, <x'-azobisisobutyronitrile (HZ = 106 "C). Preferably these polymerization initiators are used in an amount of 20 percent by weight based on the total amount of the polymerization initiator.

It is also possible to add a conventional, non-reactive plasticizer to the liquid starting mixture for vinyl chloride polymers in an amount up to 50, preferably add up to 30 percent by weight. Examples of these non-reactive plasticizers are Phthalic acid esters, such as phthalic acid dibutyl ester, -diamyl ester, -dimethoxyethyl ester, -dibutoxyethyl ester, -dicyclohexyl ester, -dihexylester, -butyloctylester, -di (noctyl) ester, -di (2-ethylhexyl) -ester, -diisooctylester, -didecylester, -didoc'ecylester and -butylbenzylester, Phosphates, such as alkyl diphenyl phosphate and tricresyl phosphate, and other non-reactive plasticizers, such as the dicapryl, didecyl and di-2-ethylhexyl esters of adipic acid, succinic acid, azelaic acid and sebacin

acid. In addition, common plasticizers for vinyl chloride poly-nitride from polyester or epoxy can be used Use type and chlorinated paraffins together with the aforementioned non-reactive plasticizers will. A plasticizer is preferably used, which reduces the flowability and shelf life Polyvinyl chloride plastisols not affected. These non-reactive plasticizers can also be used in Forrr mixtures of at least two of these compounds can be used.

The non-reactive plasticizer is added to the liquid starting mixture to adjust the viscosity; Mixture to control the enthalpy of reaction during curing and to improve flexibility: added to the cured molding.

The starting mixture can also contain stabilizers, pigments, fillers, polymerization inhibitors, Lubricant, viscosity regulator. Contain reinforcement material, such as fiberglass, and other additives To improve the surface properties of the fully cured product, the liquid starting mixture incorporated preferably about 1 to 5 percent by weight of a lubricant. Preferred Lubricants are stearic acid and zinc stearate. Magnesium stearate. colloidal silicon dioxide and Mearic acid n-butyl ester. The first four lubricants mentioned are available as a powder at room temperature and are therefore preferably used in small quantities, since the incorporation of large amounts leads to an abrupt increase in viscosity in the liquid Mixture would drive. Stearic acid n-butyl ester * at barely a temperature in the liquid mixture and soluble has no negative influence on the viscosity and the Viscosity stability of the starting mixture.

The liquid starting mixture is through a low Viscosity and characterized by a smaller change in viscosity during a long storage run. In addition, it remains stable for a long time, so various additives can be dispersed will. It turns out that the mixtures can be processed in exactly the same way as usual unsaturated ones Polyester resins. This is why% s possible before the transfer of the liquid mixture > Pretreatment in the partially hardened state to carry out, which make use of the flowability of the mixture. This means that fittings various shapes can be obtained and the range of application of the fittings is very large. For example, st partially cured plate n.atenal. obtained by impregnating a glass cloth or a glass mat with the mixture particularly valuable.

In conventional processes for the Production of glasaserverstarkten plastics (GRP) dureh Impräinie- "ί ^£ ^ ^{Cbe or} glass mats with liquid," T .-; ™ resins, for example, by placing and on it is _spruheni difficult the process automat cally or continuously carry out and Per-

fL ^ei p ' ^Ch , " ^{Quality or} mass-produced products to be supplied when impregnating glass fabric or

Sr »Mi ü ¹ - ' ^{1 that obtained} according to the invention

f; To ⁵ * ¹¹ ^ "molding composition is anyway a mechanization of the manufacture of fiberglass-Schichtstoffcn by -enormen the partially hardened molding material. Em further advantage of the invention is ^ n, ''? ^{'S l1üs} sigen starting mixture prepared partially cured molding compositions in powder or granular form used be able.

The following processes can be used to produce the liquid starting mixture:

(1) A vinyl chloride polymer powder is in a solution of an unsaturated polyester in a monomeric vinyl compound is dispersed, and the obtained dispersion is treated with a polymerization initiator offset.

<2) A vinyl chloride polymer powder is dispersed in a solution of an unsaturated polyester in a monomeric vinyl compound and a reactive plasticizer, and a polymerization initiator is added to the resulting dispersion.

(3) A solution of an unsaturated polyester in a monomeric vinyl compound is mixed with a Plastisol mixed by dispersing a vinyl chloride polymer in a reactive Plasticizer has been prepared, and the resulting mixture is treated with a polymerization initiator offset.

(4) A solution of an unsaturated polyester in a monomeric vinyl compound and a reactive plasticizer is mixed with a plastisol, which is made by dispersing a vinyl chloride polymer has been prepared in a reactive plasticizer, and the obtained A polymerization initiator is added to the mixture.

To produce a liquid starting mixture with a low ¹ × viscosity, a plastisol is preferably first produced by dispersing a vinyl chloride polymer in a reactive plasticizer, and the plastisol is then mixed with a solution of an unsaturated polyester. A process in which a vinyl chloride polymer is brought together directly with a monomeric vinyl compound is not expedient since the vinyl chloride polymer suddenly swells and gels in the process.

In the process according to the invention, the liquid mixture produced in this way is the aforementioned Contains ingredients in the aforementioned quantities, first at temperatures of 80 to 160 ° C heated so that only a partial hardening takes place. Then it is taking shape too a non-sticky, solid-like mass, which is cooled by heating to temperatures of 120 to ISO C can be fully cured.

The extent of the "partial hardening" can be determined by the transparency and the hardness of the partially hardened Determine molding compound. As the liquid mixture hardens, the total light transmission decreases zn, while the turbidity value decreases. For fully hardened fittings the total light transmission is 70 to 95% and the haze value 5 to 20%. On the other hand, the Total light transmission of the partially cured mass 40 to 70% and the haze value 50 to 95%. The transmission and haze values are determined in accordance with Japanese Industrial Standard (JIS) No. 6714.

The hardness increases as the liquid mixture hardens. The completely hardened one Product has a Rockwell (R) hardness of about 90 to 125 and a Barcol hardness of 60 to 75. The hardness of the partially cured molding compound is between 20 and 95, measured according to the "spring-type" hardness test according to JIS K-6301 (physical test method for vulcanized rubber). With degrees of hardness of less than 20, the three-dimensional crosslinking is inadequate and the mass is almost fluid. For this Basically, molding compounds of such low hardness are difficult to handle. For hardnesses of more than 95, measured according to the aforementioned test method, the plastic deformation of the mass is low, which is why the shaping cannot be carried out in a satisfactory manner. Are particularly preferred partially cured molding compounds with a degree of hardness

ίο from 70 to 90, measured according to the aforementioned test procedure. Molding compounds of such hardness have a non-sticky, solid form and no liquid character. For this reason, they can be brought into the desired shape by cutting or bending.

It is believed that the partially cured molding compositions of the invention have a low crosslink density. Therefore they are not flowable, but plastically deformable. They are also stable for a long time (generally more than three months at Room temperature). It is also assumed that the partially cured molding compositions mainly are formed from the unsaturated polyester and the monomeric vinyl compound. In the process of US-PS 35 57 046 the solid-like state is mainly due to swelling (gelation) of the vinyl chloride polymer caused by the action of the reactive plasticizer or the monomeric vinyl compound. In the method according to the invention the production of a solid-like molding compound is mainly based on the type of heating process and the heating temperature suitable to achieve slow activation of the polymerization initiator and partial curing to evoke in a desired time. A second factor is the choice of temperature that can promote swelling of the vinyl chloride polymer to some extent. In the procedure of the aforementioned US patent must be used for quilting the vinyl chloride polymer be heated to a sufficiently high temperature for a sufficiently long time. This is the activation of the polymerization initiator during the swelling of the vinyl chloride polymer as well as possible inhibited. In the process according to the invention, there is a "partial curing" and in the process the aforementioned US patent reached a "swollen or gelled" state.

The partially cured molding compositions of the invention have a crosslinked structure to a certain extent present. Therefore, evaporation or migration of the monomeric vinyl compound or the Prevents reactive plasticizer, and the result is a non-sticky surface with good machinability. In addition, no precipitation occurs during storage.

The fully cured products which can be produced from the molding compositions of the invention have eir Framework made of the unsaturated polyester. Its structure differs significantly from the product with low crosslinking density, which is achieved by adding a reactive plasticizer or a combination a reactive plasticizer and a monomeric vinyl compound to form a vinyl chloride polymer arises (namely the product of the aforementioned U.S. patent). More precisely, the hardness are dimensional stability in heat, mechanical in order chemical strength of the End products produced by molding compounds correspond to the properties of unsaturated polyester resins in a similar manner

similarly during the properties of the products obtained according to the aforementioned U.S. patent which are inylchloridplastisolen ^v of fittings made.

As already mentioned, the partially cured molding compound of the invention has a loose, crosslinked, three-dimensional one Structure (low crosslinking density) and contains a considerable number of reactive Double bonds. These remaining double bonds can be seen in the IR absorption spectrum prove.

For a more detailed explanation of the “partially cured” state, the results of the Differential analysis compiled.

F i g. 1 shows the thermogram of a liquid mixture of the invention made as follows:

A test tube is charged with 110 mg of silicon dioxide and 100 mg of the liquid mixture A described below and heated. As soon as the temperature reaches 120 ^° C., the supply of heat is interrupted. The maximum A in FIG. 1 shows that an exothermic reaction takes place at this point. The maximum A thus represents the partially hardened stage. On further heating, a further maximum B is observed, which is also shown in FIG. l is shown. This maximum B is an expression of the de during complete curing; Mixture exothermic polymerization reaction taking place.
F i g. 2 shows the results obtained in the thermal differential analysis of liquid mixtures which, according to the invention, are either partially cured and then heated (curve C) or heated continuously without initially partially closing them

ίο harden (comparison curve D). In both cases, an exothermic polymerization reaction is observed at temperatures of 150 to 200 ^° C., but in the case of the partially cured mixture, both the temperature difference Δ T and the temperature difference that is released are observed

Thermal energy Δ Η smaller.

The partially hardened stage is not only characterized by hardness and transparency, but is also characterized by the ratio of the heat energy released in the case of passing through a partially hardened stage (curve C) to the heat energy released in the case of direct hardening (curve D)

This ratio of the heat energies released at temperatures of 150 to 250 ^{0 C is through}

as the following formula:

ρ. ,. u-1 emic · _ IH of the partially cured stage passing through G s

fcntnalpievernaltnis - _{jH des} J ₃₅ p ^ «,,, _hardened stage of non-continuous mixture

If the substance decreases before it fully cures, the viscosity increases and the polymerization increases will be interrupted. This creates a non-sticky, partially cured molding compound which no longer has the odor of the monomeric vinyl compound.

When the partially cured molding compound obtained is heated to 120 to 180 ^° C., it cures completely.

Since partial curing of the mixture is provided in the process of the invention, the final curing can be carried out at relatively low temperatures (120 to 180 ^° C.) in a short time. In addition, the degree of polymerization can be easily controlled. The molding compositions of the invention also contain a vinyl chloride polymer, so that they are superior to unsaturated polyesters in that they hardly shrink in shape and the moldings obtained have hardly any warpage or cracks. The molding compositions of the invention are thus superior to the known unsaturated polyesters in their processing properties and in the properties of the molded bodies produced.

From the foregoing it can be seen that the following three points in the preparation of the partially cured Molding compounds from the liquid starting mixture are important:

(1) temperature and heating method,

(2) interrupting the curing reaction and

(3) Selection of the polymerization initiator.
This is explained in detail below.

The enthalpy ratio is in the range from V ₄ to V ₈ -

F i g. 3 shows the results of the differential thermal analysis of a liquid mixture of a vinyl chloride polymer and a reactive plasticizer according to US Pat. No. 3,557,046 (curve E) and of a semi-solid mixture obtained by partially gelling this liquid mixture (curve F). From Fig. 3 shows that, regardless of whether the mixture is partially gelled or not, similar enthalpy curves are obtained. This means, however, that the mixtures known from the US patent contain in the semi-gelled state only vinyl chloride polymer particles swollen by the reactive plasticizer and that this swollen state is fundamentally different from the partially hardened state of the invention, namely by the loosely crosslinked, three-dimensional state.

In the process of the invention, external heating initially results in absorption of the monomeric vinyl compound and / or the reactive plasticizer on the vinyl chloride polymer when the above-described liquid mixture is prepared, optionally mixed with additives and then heated to temperatures of 80 to 160 ^° C heated. In the next stage, the polymerization is initiated by the radicals released during the decomposition of the polymerization initiator, and the free monomeric vinyl compound and / or the reactive plasticizer and the unsaturated polyester are adsorbed on the higher molecular weight vinyl chloride polymer by external heat input and the heat of polymerization. At the same time, a slightly crosslinked, three-dimensional structure is formed by copolymerization, so that the viscosity of the mixture increases sharply and at the same time the curing rate decreases due to the diffusion of the monomeric vinyl compound and / or the reactive plasticizer, the polymer radicals and the initiator radicals. If you cool the mold

(1) Temperature and heating method

If the mixture is in a form that allows a discharge the heat of reaction prevented so that, for. H. the temperature of the mixture in the course of the reaction is above room temperature, there is complete hardening because the reaction to runs quickly. On the other hand, if the mixture is in

a form in which the heat build-up is dissipated well, e.g. B. as a film or plate, or you choose one Heating mode with little heat transfer, it becomes complete even at room temperature Hardening time is extended. To continuously maintain a partially hardened stage, therefore the type of heating and the shape of the mixture must be selected accordingly.

(2) Interruption of the curing reaction

The partially cured molding compound is then cooled and in this state at room temperature held. To make this possible, the curing reaction must be interrupted. One can gradually or cool quickly; the optimal cooling method depends on the type of starting mixture. Allegedly the interruption of the reaction proceeds according to the following mechanism.

The vinyl chloride polymer contained in the liquid starting mixture as a component is at higher temperatures with other components such. B. the monomeric vinyl compound and / or the reactive plasticizer solvated so that it swells and absorbs the vinyl compound and / or the reactive plasticizer. In this way the hardening reaction is delayed and at the same time the diffusion of the polymerization radicals is made more difficult due to the increased viscosity of the mixture. If the partially cured molding compound obtained is cooled, the viscosity increases further and finally the curing reaction is interrupted. The conversion of the liquid starting mixture to the partially cured molding compound is therefore carried out at a temperature which allows the vinyl chloride polymer to swell by the monomeric vinyl compound and / or the reactive plasticizer. The reaction is therefore usually carried out at temperatures above 80 ¹ C, but the statements under (1) must be observed.

(3) Selection of the polymerization initiator

If a polymerization initiator which decomposes at low temperatures is used for curing, for example benzoyl peroxide (HZ = 130 ^° C.) and the reaction system is kept at 120 ^° C., the reaction proceeds too quickly and the partially cured stage cannot be maintained. If, on the other hand, the curing is carried out at 60 ^° C., the molding composition cures completely without the vinyl chloride polymer swelling.

If a polymerization initiator that decomposes at higher temperatures is used, e.g. B. tert-butyl hydroperoxide (HZ = 179 ° C) and if the reaction system is kept at 120 ^c C, the curing reaction can be terminated by cooling the mixture after a certain heating time, the time required to set the partially cured stage from the The type of liquid starting mixture and the heating method.

The following is the manufacture of special fluids Mixtures explained.

Preparation of a liquid mixture A.

Isophthalic acid maleic anhydride, propylene glycol and neopentyl glycol are in a molar ratio of 1: 1: 1.1: 1.2 to form an unsaturated polyester an acid number of 24, an average degree of polycondensation of 13 and a number average molecular weight of 1330 [in the following »unsaturated polyester (a)«] implemented.

Separately from this, 62.5 parts by weight of a vinyl chloride polymer are used for paste production (Vinyl chloride homopolymer with a degree of polymerization of 1700), 37.5 parts by weight of trimethylolpropane trimethacrylate and 4.4 parts by weight of a zinc-cadmium-barium stabilizer for polyvinyl chloride in fed a mixer and thoroughly 20 minutes

ίο stirred to the powdery vinyl chloride polymer to disperse. This is followed by defoaming and the mixture obtained with 100 parts of a 40 percent by weight Styrene solution of the unsaturated polyester (a) is added. This is obtained after stirring for 10 minutes liquid mixture A with a viscosity of 53 P in the freshly prepared state (measured at 25 ° C with the No. 4 rotor of a B H viscometer). After one day the viscosity is 110 P, after 10 days 116 P and after 3 months 121 P. During this period there is no phase separation or sedimentation. The example thus illustrates a method for producing a stable liquid mixture in which the plasticizing effect of trimethylolpropane trimethacrylate, which is a plasticizer for vinyl chloride polymers causes the formation of a vinyl chloride plastisol. This plastisol is then with a mixed unsaturated polyester without the viscosity of the plastisol increasing or exceedingly gelation occurs.

Preparation of a liquid mixture B

The unsaturated polyester vinyl chloride polymer and stabilizer used for the production of the liquid Mixture A used ingredients.

In the stirring mixers described above, 45.5 parts by weight of vinyl chloride polymer, 50 parts by weight of a 56.4% by weight styrene solution of the unsaturated polyester (a) and 3.2 parts by weight of the stabilizer for vinyl chloride polymers are mixed for 20 minutes with stirring to form a paste-like dispersion of relatively high viscosity. 50 parts by weight of the styrene solution of the unsaturated polyester (a) mentioned are then added to the dispersion, so that a liquid mixture B with a viscosity of 120 P in the freshly prepared state at 25 ^° C. is obtained. After 20 hours the viscosity is 121 P, after 100 hours 120 P and after 500 hours 115 P. However, after one month of storage, a small amount of a highly viscous layer separates on the bottom of the container. If the content of unsaturated polyester in the styrene solution is less than 30 percent by weight, the viscosity of the liquid mixture obtained is above 1000 P; If the content is below 10 percent by weight, it is no longer possible to produce a flowable liquid mixture. Furthermore, agglomerates of the vinyl chloride polymer particles form when the styrene solution of the unsaturated polyester is added on one side, so that the vinyl chloride polymer particles are not uniformly dispersed. For this reason, the styrene solution of the unsaturated polyester is added in two portions in the example.

The phenomena mentioned are based on the swelling of the vinyl chloride polymer by styrene.

It is known that styrene swells and gels when it comes into contact with vinyl chloride polymers Serious cause A yinyl chloride polymer is added with a large amount of styrene, it can be

609 624/216

do not prevent an increase in viscosity or gelling. On the other hand, if the vinyl chloride polymer and styrene are brought in the presence of an unsaturated one Polyester in contact with each other, it is possible to make the vinyl chloride polymer particles uniform to disperse and at the same time to prevent swelling of the vinyl chloride polymer. In particular when adding the styrene solution of the unsaturated polyester In two servings, the viscosity increases slightly in the first stage, but the vinyl ίο chloride polymer are uniformly dispersed. By adding the second half of the polyester solution the viscosity is lowered again in the second stage, with no irregular agglomerates Form vinyl chloride polymer particles.

the styrene solution of the unsaturated polyester used to prepare the liquid mixture A. was prepared (in the following "comparison mixture No. I"), are each with 1 percent by weight of tert-butyl hydroperoxide offset. The high temperature hardening properties are according to the test standard JIS K-6901 determined for each mixture. The thermostatic The temperature here is 120'C. The results are shown in Table I.

Table I.

Preparation of a liquid mixture C

In the mixer mixer described above 100 parts by weight of a solution containing 43.6 percent by weight of the unsaturated polyester (a), 29.1 percent by weight Styrene, 18.2 percent by weight of methyl methacrylate and 9.1 percent by weight of dibutyl fumarate contains, with 45.5 parts of the above vinyl chloride polymer and 3.2 parts of the above stabilizer thoroughly mixed up. After stirring for 20 minutes, a liquid mixture C with a viscosity is obtained of 115 P in the freshly prepared state at 25 ° C. After 20 hours the viscosity is 115 P. 100 hours 116 P and after 500 hours 110 P. After one month of storage, at the bottom of the container do not find any deposits. In this example, dibutyl fumarate is in the solution of the Contain unsaturated polyester, but also causes the sole use of dibutyl fumarate a uniform dispersion of the vinyl chloride polymer particles as a reactive plasticizer. at With a certain polyester and styrene content, methyl methacrylate is used in the solution of the unsaturated polyester and dibutyl fumarate, preferably in a weight ratio of the one as possible results in low viscosity of the resulting liquid mixture. The best results are achieved with one Methyl methacrylate / dibutyl fumarate weight ratio of about 2: 1.

Minimum hardness Max. Tempe time rature (min) CO 11.3 202 16.1 163 22.2 140 6.0 250

Comparative example I.

The liquid mixtures A, B and C and a styrene solution an unsaturated polyester that is similar to

45 Liquid mixture A
Liquid mixture B
Liquid mixture C
Comparison mixture I

Comparative example II

A mixture of 40 parts by weight of 1,3-butylene glycol dimethacrylate, 30 parts by weight of coarse-grained vinyl chloride polymer, 30 parts by weight of finely divided Vinyl chloride polymer and 0.3 part by weight of tert-butyl perbenzoate are added under reduced pressure degassed, a liquid mixture (hereinafter referred to as “comparison mixture No. II)” being obtained.

The liquid mixture is heated in a hot press at a mold temperature of 115 ° C. for 1 minute and then quickly cooled to room temperature. A semi-gelled, plate-shaped product is obtained 1.5 mm thick, which is light and flexible, but only semi-transparent and not very firm.

The 'liquid mixtures A, B and C and the comparison mixture No. I are each poured between two glass plates measuring 20 20 cm, so that a plate 3 mm thick is created. This is cured in a hot air dryer at 120 ° C for 120 minutes. The plate is then removed from the dryer and cooled to room temperature. The comparison mixture No. II is poured between two glass plates in a similar manner, 30 minutes in a hot air dryer heated to 150 ° C and then cooled to room temperature. The physical properties of the plates thus obtained are shown in Table II.

Table II

Properties of the panels

Liquid mixture

Liquid mixture

Liquid mixture

Comparison mixture

Comparison mixture

II

Test standard

Strength module (kg / mm ² )
Tensile strength (kg / mm ² )
Stretch limit (%)
Flexural modulus (kg / mm ² )
Flexural strength (kg / mm ² )
Rockwell hardness (R)

Izod core impact strength
(kg cm / cm ² )

Heat resistance ( ⁰ C)
Light transmission (%)
Degree of opacity (%)

287 327 335 359 325 JIS K-6919 6.01 3.19 5.86 3.14 6.33 JIS K-6919 4.79 2.33 4.16 2.11 4.59 JIS K-6919 349 330 297 361 199 JlS K-6919 12.2 5.01 10.3 12.6 4.66 JIS K-6919 125.0 122.9 122.4 126.4 102.6 ASTM D-785 1.18 1.29 1.7.1 1.57 0.23 JIS K-6911 99.7 103.6 95.0 114.2 72.0 JISK-6911 86.5 75.0 85.0 87.7 81.7 JlS K-6714 10.2 15.1 14.9 7.15 16.0 JIS K-6714

The results show that those made from the liquid components A, B and C of the invention cured moldings have physical properties similar to those of hardened moldings the unsaturated polyester. On the other hand, those from comparative mixture No. I! produced moldings far poorer properties than the cured moldings from the mixtures according to the invention or the unsaturated polyester. They not only have lower hardness and heat resistance, but also poorer flexural strength and notched impact strength as well as a less favorable flexural modulus.

20th

Preparation of liquid mixtures D, E, F, G and H from the dicarboxylic acids listed in Table III and polyalcohols are known per se

Way the unsaturated polyesters (b) to (f) are produced. These are reactive with monomeric vinyl compounds and / or those listed in Table IV Dissolved plasticizers and added to the liquid mixtures U by the above process

> o E F G and H processed. The viscosity data and Hardness properties of the liquid mixtures are also compiled in Table IV.

Table ΠΙ

Unsaturated
polyester

Dicarboxylic acid

; (Molar ratio) polyalcohol Acid number

Molecular weight

(Numerical mean)

Average degree of polycondensation

PA / MA = 1/1
IPA / MA = 1/1
PA / MA = 1/1
IPA / MA = 1/1
IPA / MA == 1/1

HD = 2.2 "

NPG / DEG = 1.1 / 1.1

NPG / EG = 0.7 / 0.4

HD / NPG = 1.1 / 1.1

NPG / PG / DEG = 0.97 / 1.08 / 0.11 1370
2460
1160
2000
1460

12 23 13 18 15

The abbreviations in Table III have the following meanings:

PA: phthalic anhydride,

IPA: isophthalic anhydride,

MA: maleic anhydride,

HD: 1,6-hexanediol,

NPG: neopentyl glycol,

DEG: diethylene glycol,

EG: ethylene glycol,

PG: propylene glycol.

Table IV

composition
(Parts by weight)

Liquid mixtures D E

60

40

40

Unsaturated polyester b

Unsaturated polyester c

Unsaturated polyester d

Unsaturated polyester ε

Unsaturated polyester f

Styrene

Methyl methacrylate

Acrylonitrile

2-ethylhexyl methacrylate

2-ethylhexyl acrylate

Vinyl chloride polymer for pastes 60

(Degree of polymerization = 2300) Vinyl chloride polymer for pastes

(Degree of polymerization = 900)

Diethylene glycol dimethacrylate dibutyl fumarate

60 60

30th 60 60 20th 40 40 20th 17.5 20th 50 40 60

100

12.5

40

Table IV (continued) 22nd 52 931 \ F. 22nd H 21 Composition 30th (Parts by weight) 3.5 3 Dibutyl phthalate Liquid mixtures G Zn / Cd / Ba stabilizer D. E. 132 97 Viscosity (poise) 142 4th 103 freshly made 4th 7th 145 143 after 20 h 145 150 155 after 100 h 2100 1280 160 after 500 h 2300 1310 21.8 193 23.5 Hardening properties 2300 1310 138 195 119 Minimum hardening time (min) 2300 1320 max.temperature ( ⁰ C) 22.7 22.8 24.7 129 128 121

The examples illustrate the invention. Ren of the example after 10 to 30 minutes, preferably

20 to 25 minutes is reached.

B e i s ρ i e 1 1 25 In the above example one thus obtains partially

(A) Production of cured molding compounds by heating over a

a partially cured molding compound for a certain period of time; the partially hardened stage

is mainly due to the transparency that

The liquid mixture A is identified with 1 percent by weight of turbidity and the hardness. When tert-butyl hydroperoxide is mixed and then heated between 30 and over a period of time, which is poured on the lower two glass plates (20 × 20 cm), the 3.0 mm limit of the required heating time is separated from each other. To check the surface of the partially cured curing process obtained, the molding compound then becomes slightly tacky; However, if one is heated for a longer period in a hot air dryer at 120 ^° C. and after a period of time, the stickiness decreases and on heating 10, 20, 25, 30, 45, 60 minutes, 2, 2.5 and 4 hours 35 up to the upper time limit you get one not examined. After 10 minutes the mixture is still sticky, partially cured molding compound. The not liquid, after 20 or 25 minutes it is in an almost polymerized Styrof in the partially hardened solid state, ie partially hardened. After 30 to the molding compound is relatively stable and does not volatilize. The molding compound has solidified for 60 minutes, however, even in the partially cured one obtained, it is not yet fully cured. Only after 40 molding compounds have the characteristic odor of styrene for 2 hours or more are completely cured compounds no longer detectable. The moldings obtained in this example. The light permeability and the cloudy, partially cured molding compound only smells like the individual moldings are like tert-butyl hydroperoxide. In the following, the test standard JIS K-6714, the hardness of the partially hardened molding compounds produced in this example by heating for 25 minutes according to test standard JIS K-6301 with 45 set molding compound is determined as a partially hardened molding compound and spring hardness tester. The mass achieved is X ”.
The results are summarized in Table V.

(B) manufacture
of a fully cured molded body

50 The partially hardened molding compound is further Heated to 120 ° C. for 4 hours as described above. From the results listed in Table VI it can be seen that the fully cured molded body obtained (sample 7) has its own physical properties Shafts is similar to the fully cured molded body (sample 6) obtained by continuous; Heating without intermediate cooling was produced.

The flexural modulus, the flexural strength, the Rockwell The gelled product from the comparative molding massi

Hardness, light transmittance and the haze level 60 no. II from Comparative Example Il is another 240 Mi of more than 30 minutes heated mixtures are heated in utes to 120 ⁰ C. The molding obtained is compiled in Table VI. The values in brackets stated in the rubric is cloudy and has no improved physical properties. When heated for 30 minutes at 150 ° C., the results do not relate to the breaking strength, but rather similar properties result to those in Table II with regard to the bending limit. This is based on the fact that the specimen does not break in the flexural strength test, however the fully cured molded body does not break. z. B. Lower hardness and heat resistance. From the results in Tables V and VI, it can be seen from the partially cured molding compound that the partially cured stage of the molded body produced in the process.

Table V 20 min. 25 min. Heating time 48.3% 55.8% Light transmission m το /
"■ y ¹ · / 0 88.7% Degree of opacity 78 85 hardness 0.190 0.175 Enthalpy ratio

Table VI

sample

Heating time (min) 30 45 60 120 150 240 240

Flexural modulus (kg / mm ² ) 6.80 219 213 336 349 310 318

Flexural Strength (kg / mm ² ) (0.383) (7.11) (7.99) 12.1 12.2 12.1 12.3

Rockwell hardness (M) 42.0 56.5 72.3 96.0 94.4 98.7 98.3

Light transmission (%) 72.5 80.0 84.2 86.5 87.2 86.9 86.5

Degree of opacity (%) 63.0 45.3 21.3 10.2 11.3 10.0 12.1

B e i s υ i e 1 2 can impregnate glass mats. One works here

15 according to the usual process for the production of glass fiber

From a 15 χ 15 cm large and 3.0 mm thick reinforced plastic, e.g. B. after the hand lay-up plate of the partially cured molding compound X is proceeded. It is therefore possible to produce an ashtray-shaped, hardened, glass fiber-reinforced molding compound, which is partially cured under a load of 50 t, by Imger moldings 3 cm deep. A pressure impregnation of glass fibers with the liquid output of about 5 kg / cm ² in the press pressure is sufficient if the mixture is heated for ^{3 minutes at 150 ° C and then partially cured.} Establish the pressing process. »

is based essentially on a plastic deformation and thus differs from the usual liquid mixture A, 2 weight compression deformation of flowable polymers. No high pressures are required for the molding of n-butyl stearate, 5 parts by weight of a yellow molding of the partially toned according to the invention, 1 part by weight of p- (m) -mententhan hydroperoxide cured molding compounds, and 0.2 part of benzoyl peroxide is produced with the aid of one of the methods z. B. in the processing of styrene impregnation roller for the hand lay-up process on maleic anhydride copolymers, so that you can use a smooth glass fiber fabric in a lot of customary molds. However, it is advisable that the glass content is 50 percent by weight of the partially cured mold described above. The impregnated glass fabric is suitable for protective mass not for the production of complicated form between two 5 μm thick films of stretched poly body, since the pressing process, in contrast, is propylene and then heated to 120 ° C for 20 minutes in a hot air dryer for injection molding on a plastic deformation. This is what it is based on. The partially cured molding compound X can be removed from the dryer and, in contrast, advantageously cooled to form large-area molded bodies 35 temperature. A partially cured molding compound is obtained in a molded form with small elevations and depressions. When drying. The aforementioned ashtray temperature of 120 "C is the heating time. The shaped body has a flexural modulus of usually 15 to 25 minutes, at 130 ^° C. 7 to 340 kg / mm ² , a flexural strength of 11.5 kg / mm ^{2 and} 10 minutes at 14O ⁰ C for 4 to 5 minutes. to drain and a Rockwell hardness (R) of 124.3. also at 40 cooling, the sample is only the furnace entnomviermonatigem standing the partially cured men and allowed to stand at room temperature. in the case of molding composition can this At the same temperature, the partially cured molding compound is used as a protective film for the same pressure and the same heating conditions, the stage partially cured to a molding with similar properties is achieved at 12O ⁰ C in 6 to 7. 45 grooves in this case the course of the reaction

Example 3 is not uniform, and a partially cured one is obtained Molding compound, the z. B. in terms of hardness

The partially cured molding compound X has heterogeneous properties, which are presumably finely ground with the aid of a jet mill and 100 physical properties, e.g. B. the oxygen parts of the particles obtained with a particle permeability, 50 of the cell glass are to be attributed, size of less than 0.15 mm with 30 parts by weight of calcium carbonate and 20 parts by weight. In the following, the partially cured glass fibers of 6.35 mm length are mixed thoroughly. Molding compound in this example is referred to as “plate-shaped, par-With this mixture, the molding press made from partially cured molding compound Υ”. The shape game 2 charged for the production of ashtrays, 55 mass Y has a thickness of about 0.25 mm.
and by heating for 3 minutes at 150 ° C. In the case of impregnation of a glass fiber fabric under a pressure of 30 kg / cm ^2, moldings can be produced with the liquid starting mixture. A different molding press was used as fillers, such as calcium carbonate, clay, aluminum in Example 2, because the particles of the molding compound X, which is partially hardened into the hydroxide and antimony trioxide, remain in the mixture at higher temperatures.

doors come into closer contact with each other and A special example of such a mixture

so the melt adhesion of the particles by heating looks like this:

and their union in the course of the parts by weight of hardening

reaction can be accelerated. Liquid mixture A 100

_D. . ,. 6 ₅ styrene 10

^{B e} ' ^s P ^{x e l 4} calcium carbonate 30

The liquid starting mixtures used are colloidal silicon dioxide 2

low viscosity. so that you can use them with glass fabric or dicumyl peroxide 1.5

Example 5

IS

A glass fiber laminate of 3 mm thickness is prepared by superposing the plate-shaped pieces 12, partially cured molding compound Y for 3 minutes and then pressing at a pressure of 3 kg / cm ² and 15O ⁰ C in a hand press. Although the pressure is relatively low, the individual layers are sufficiently bonded. The laminate obtained has a flexural strength of 21.0 kg / mm ² , a flexural modulus of 2000 kg / mm ² and a Barcol hardness of 55.

By inserting a metal wire between the plate-shaped, partially cured molding compounds Y and then pressing is used to produce a laminate. The metal wire is completely in the laminate embedded. Such a molding process is to increase the mechanical strength of the glass fiber reinforced Laminate and suitable for making composite laminates that break when broken do not unfold into individual parts.

Example 6

The impregnated glass fabric covered with a protective film from Example 4 is processed directly into a partially cured molding compound by heating in a hand press. In this method, heating is preferably 2 to 3 minutes at a platen temperature of 120 ° C. In the production of plate-shaped, partially cured molding materials from liquid mixtures B and C is heated by the same procedure 1 to 2 minutes at a platen temperature of 120 ^c C receives or 2 to 3 minutes at a platen temperature of 110 C. In all cases, ^c piattenförmige, partially cured Formmassei having excellent properties.

Example 7

It becomes a hemispherical shaped body with an inside diameter of 177 mm, an outside diameter of 180 mm, a thickness of 3 mm by a height of 90 mm with the help of a 50 t press manufactured. There is a half on the lower press platen

ίο attached spherical male mold and twelve 20 X 20 cir individual pieces of the plate-shaped, partially hardened molding compound Y are placed on top of each other on the mold, at 3 minutes! i * srr! Pr. »C ^ r; :: r; for eir.err pressure of 5 kg / cm ² and a mold temperature

1-0 C obtained a hemispherical molding The piattenförmige, partially cured molding compound \ is thus three-dimensional to a molding having! curved surface can be processed. When producing a U-shaped molded body from two

»Ο dimensional sections is the minimum Inner diameter 3 mm. The glass fiber material does not break during the manufacture of these moldings.

Example 8

As the above-mentioned liquid mixtures D, E, p, ^{and H} are partially cured under the conditions listed in "Table VII and then pressed using a hot air dryer according to Example 1. The curing takes place in

measured Example 2 using a mold and a 3U-t press. The deformation conditions are also given in Table VII. When checking the The results listed in Table VI are achieved

Table VII

Liquid mixtures

Quantity (parts by weight)

Polymerization initiator
tert-butyl hydroperoxide
p- (m) methane hydroperoxide

100

100

100

100

Benzoyl peroxide 120 120 ι on 0.9 0.9 20th 25th 20th 0.1 0.1 Conditions of partial Curing Temperature, ( ⁰ C) no no Heating time (min) 0.205
55.4 0.180
46 3 no
0.185 120
30th 130
25th Properties of the partial 47.1 51.3 63.2
62.6
94.5 hardened molding compound 78.3 86.5 Stickiness 1 CfI Enthalpy ratio
Hardness according to the spring method 150 150 1 _7U
C, no
0.105 no
0.165 Light transmission (%) 5 5 J
3 71.5 31.6 Degree of opacity (%) 3 3 45.3
72.3 63.3
93.2 Shape conditions Temperature ( ⁰ C) Pressure (kg / cm ² ) 150 160 Molding time (min) 5
3 5
3

Table VII (continued)

Liquid mixtures
DE

Properties of the completely
oushardened molded body

Flexural modulus (kg / mm ² ) 357 155 250 135 312 Flexural strength (kg / mm ² ) 12.1 4.3 7.5 3.8 10.3 Rockwell hardness (R) 124.2 110.3 115.5 102.0 116.3 Translucent wedge (%) 75.6 82.5 83.6 84.0 73.3 Degree of opacity (%) 40.0 13.6 14.5 15.8 21.0

Example 9

From 40 parts by weight of styrene and 60 parts by weight of an unsaturated polyester, which is composed of the in If the ingredients listed in Table VIII are composed, a solution is prepared. Be on it 100 parts by weight of a vinyl chloride homopolymer for pastes with a degree of polymerization of 1650 dispersed in 160 parts of the solution obtained and with 5 parts by weight of an organotin stabilizer for vinyl chloride polymer, 3.6 Gev.ichtstcilen tert-butyl hydroperoxide and 60 parts by weight of styrene are added.

For each of the liquid mixtures, the time course of the viscosity is observed in which the Apparent viscosity at 25 ° C. in the periods mentioned with the aid of a BH rotary viscometer (Rotor 5) determined. The results obtained are shown in Table IX, which also includes the thixotropy index is given as the ratio of the apparent viscosity at 4 rpm to the apparent viscosity defined at 20 rpm is.1.

Table VIII

Unsaturated composition
Pülyest: r

Molecular ratio of

fed in

Components

properties

Excess acid number

Glycol component Molecular weight Average poly (number average) degree of condensation

G PA / M A = 1/1 8th Phthalic anhydride, 24 1230 12th NPG = 2.16 Isophthalic acid, H PA / ΜΑ = 1/1 10 Adipic acid, 17th 1370 12th HD = 2.2 Maleic anhydride. i IPA / MA - = 1/1 8th Propylene glycol, 25th 1400 13th NPG = 2.16 : Neopentyl glycol, j AD / MA = 1/1 8th 1-6 hexanedioi. 17th 2340 19th PG / NPG = 1.08 / 1.08 k IPA / MA = 1/1 8th 28 1720 18th PG / NPG = 1.53 / 0.63 1 IPA / MA = 1/1 8th 20th 2190 22nd PG / NPG = 1.08 / 1.08 m IPA / MA = - 1/1 8th 28 1980 20th PG / HD = 1.08 / 1.08 The abbreviations in Table VIII mean: PA: IPA: AD: MA: PG: NPA HD:

Table IX

Flow behavior of the liquid teeth and viscosity dependence over time

Fluid Unsaturated eggs Viscosity according to 1 d 3d 5d Hd 25 d Thixoiropia mixture polyester 28.9 30.9 31.6 35.1 34.8 index (after
5d) No. 5h 29.7 32.4 33.8 37.7 39.8 LOl i G 26.8 44.5 48.1 48.1 49.0 49.3 1.00 J ΰ 25.4 21.0 21.1 21.2 21.2 21.2 1.03 K i 32.5 315.0 321.4 329.0 341.1 346.6 1.03 L. j 19.3 96.8 109.5 111.6 111.6 119.6 2.87 M. k 303.2 56.8 59.6 61.5 64.7 69.1 1.01 N 1 68.9 1.00 O m 43.5

vniwS ^? I ^ ^ f "' ^{that the} above liquid mixtures I to O are used when cleaning agents are used

neopentyl glycol or 1,6-hexanediol or a ₃ o according to Example 1 for 25 minutes by heating to S oSe% ⁰¹⁶ 6H ^ H ^{15, M 20 "oI} r ^centered Ne ^ pentyl 120 ° C in partially cured FoLmaSn L _ge g ykol or 1,6-hexanediol, converts to the production. Subsequently, these by 3minütic "of an unsaturated polyester for the liquid starting heating to 15O ⁰ C to fully cured form ΑΓϊΓ ϊ ^ ⁸⁶ ° P ^{ThlXOtr ie U" d a nid> kö} bitt Di FköibSS '

g finally cured form

^ ΑΓϊβΓ ϊ ⁸⁶ · ^T _H ^hlXOtr _K ° P ^{ie U} " ^{d a niedri} > ^kör P" «elaborated. Die FormköiperbesitShnSe '

V skosiu are possible, with also the ^ ₅ properties like the sample 7 in table VI viscosity hardly changed over time.

For this purpose 3 sheets of drawings

Claims (2)

Patent claims: 1. Partially cured molding compounds, consisting essentially of a loosely crosslinked polymer with a three-dimensional structure - made of an unsaturated polyester resin, a Vinyl chloride polymer and optionally a reactive plasticizer - and a polymerization initiator, characterized in that the polymer consists of a mixture of (A) 5 to 70 percent by weight of an unsaturated polyester having an average degree of condensation of at least 4 and a number average molecular weight of at least 1000, (B) 20 to 70 percent by weight of a monomeric vinyl compound and / or a reactive one Plasticizer, (C) 10 to 65 percent by weight of a vinyl chloride polymer and (D) 0.2 to 3 percent by weight of a polymerization initiator has been obtained, and a hardness of 20 to 95, measured by the »spring-typee method, a Has total light transmission of 40 to 70% and a haze of 50 to 95%. 2. A method for producing molding compositions according to claim 1, characterized in that a liquid mixture that is obtained by thorough stirring and mixing of a (A) 5 to 70% of an unsaturated polyester having an average degree of condensation of at least 4 and a number average molecular weight of at least 1000, (B) 20 to 70 percent by weight of a monomeric vinyl compound and / or a reactive one Plasticizer, (C) 10 to 65 percent by weight of a vinyl chloride polymer and (D) 0.2 to 3 percent by weight of a composition containing a polymerization initiator