DE2324061A1 - HOT-CURING, UNSATATURATED POLYESTER MOLDING COMPOUNDS - Google Patents

Description

CIiLMISCHE 17SKKE HÜLS AG
- RvSP PATENTS - ·

Jj-370 üarl, May 11, 1973 7465 / Go

Our reference: O.Z. 271

p 23 I.

Heiflh arfrende, _ urtftesättrl p te Polyes / fc

The subject of the present application is a hot-bonded polyentex ormmasso, consisting of

1 . an unsaturated polyester

2. one with 1 »mixed polymerizable vinyl moiioinoren

3. 1 to 15 percent by weight - based on the sum of

1 . and 2. - Polystyrene dissolved in Monostyi'ol with a

K «Vert from hO - 100
k, an alttivator ^ 'ß'cem, which above 80 C anspx-in ^ t

and
5 * customary auxiliaries and additives, such as inhibitors, mineral fillers or glass fibers.

It is known that P ο lye ρ t o.rfom!: Na ssen to sarnie on with G-iiis fibers as well as other mineral fillers by liei.Oyr.-o ^ .son to valuable Gobrauchsarti?: (-. B: wie to process body panels, chairs., shells or Gq häusar, an ilen the cured Tailored often interferes ¹ a rough, wavy ö surface which must be smoothed by reworking. Disturbing is further shrinkage, d5.e insbesoride-re to moldings with Contrasting ribs result in uneven surfaces and insufficient dimensional accuracy.

Γ-s is known that mar. Polyester moldings with reduced shrinkage due to to sat. from thermoplastics such as polystyrene or styrene-Γ-opolyiaerisaten can be obtained (.Kunststoff-Adviser 10 (197O), pages 962-963).

4098A7 / 1 008

BATH ORIGINAL

- 2 - OZ 271fr

May 11, 1973

It has been shown by our own experiments that the addition of approximately 10 yj polystyrene with commercially available styrene-containing polyester resins mindort Although the shrinkage of glass fiber reinforced moldings etvas, but not completely prevented. As a result, glass fiber-reinforced molded parts continue to be unsatisfactory in terms of surface gloss and dimensional accuracy.

From laid-open specification 1 803 3fr5 and from US patent specification 3 503 921 is known by adding a polymer dissolved in styrene, which is at least partially derived from styrene, vinyl chloride or diallyl phthalate, from an unsaturated polyester resin To produce molding compositions with reduced shrinkage. Polyester resins are used here, preferably those containing ether groups Diols such as diethylene glycol and dipropylene glycol as well as exclusively Contain maleic acid as a dicarboxylic acid. With these resins, however, no completely shrink-free or easily expandable molding compositions are obtained.

From the German Auslegeschrifts 1 008 fr87 and 1 II5 923 it is known, high-percentage styrenic solutions thermoplastic Polymeric - like styrene as an anti-shrink agent in polyester compounds to use. These polyester compounds, the commercially available polyester resins are hardened at room temperature by cold pressing; they are "cold-curing polyester resins" according to claim. This distinguishes them essentially from the thermosetting polyester resins of the present invention: The difference is based on the fact that shrinkage occurs when polyester molding compounds are cured occurs both through the cooling and through the polymerization, i.e. the shrinkage is about twice as high and therefore more difficult to overcome than with cold hardening. Means the teaching of these patents could not be used for hot curing shrink-free curing moldings are obtained.

It is also known from Offenlegiingsschrift 2 06fr 1 k-8 , polyester formulations which, in addition to an unsaturated polyester, have a

40 9847/1008

Tu] Ti 973

saturated polyester, for example Polyprop3 ^r lenadipat acid as anti-shrinkage agents, such as to add as an additional component a thermoplastic polymer such as polystyrene, which is intended to prevent carve out oes saturated polyester during dci "ü-färniehärtmig. disadvantage of this method is that a dei-like Mixture of three polymers is incompatible The components are therefore only mixed together shortly before processing, which requires expensive storage.

"Furthermore, it is known powdered POL3 ^r st3? Add -rol unsaturated molding compounds as filler. In this case, it has been found _for that the polystyrene is not detached from the existing styrene monomer, also show the molding compositions does not have the desired effect in the sense of the invention.

The aim of the invention was, by the use of unsaturated polyesters (i) from certain, ausgeväh on the type and quantity ratio · ¹ th dihydric alcohols heißhärtendo produce molding compounds that without shrinkage - if possible under expansion vc-n 1-5 by volume of ^ * ■ hardening and molding parts with an excellent surface, water-like appearance and good dyeability to be produced.

The task at hand is solved by such unsaturated polyester f-or-ji! " masses dissolved in which the unsaturated polyester 1. a I'ondonsationsprodulct is off

A. one or more dicarboxylic acids, where iaiiiclestc ^ri .s 50 M0I-50 of the acids are CO ₉ ß-unsaturated dicarboxylic acids and

B. a mixture of

I. ethylene glycol and

II. From Diolen with a soluble corona provider from 10 to 15t

409847/1008 ORIGINAL BATHROOM

- h - ο.ζ. 2714

May 11, 1973

where the r-ittle.ro solubility parameter of the GGinisc? ies from I, and IX. - on the basis of the weight fractions of the glycols - between 15.1 and 16.7.

The pleasure of unsaturated polyester 1. contained in the ii-'iurolroir.poneivfce Funarsäui-e, maleic acid or maleic anhydride, fc ^T ',! K; r itaconic acid or citraconic acid. Up to 50 / o of οί-, β-unsaturated dicarboxylic acids may copolymorisationsfähigen by saturated dicarboxylic acids such as ^1, especially o-phthalic acid or o ~ Phthalsäux-ermhyärid, further tetrahydrophthalic acid, isophthalic acid, or Tetrachlorphthaisäure Ilexachlorendomethyl ent etrahydrophthal acid oc \ ov your Anhydi " ide be replaced.

In particular, the unsaturated polyesters contain fumaric acid (or maleic acid) and phthalic anhydride in a molar ratio of 1 »5 ϊ 1> foriior 2: 1 or 3! 1 ♦ Particularly hoclirealctive polyester · contain these components in a molar ratio of 5 ' 1 or exclusively maleic acid O&QV fumaric acid as diccirboxylic acid.

It has proven to be useful for characterizing the diol content of the unsaturated polyester 1. Use the solubility factor c5 = Valv / v 'ζυ, where δEv is the heat of evaporation and V is the volume. The derivation of this formula and examples for the application of solubility parameters can be found, for example, in paint and varnish no. 9 ₉ 1972, pages 813-822. The numerical values used in the following were taken from J. Paint Technol. 42 (197O), Ni. 5 * 1-1, »page 79 - 114, taken.

In addition to ethylene glycol with a solubility parameter of $ ~ 17.05, the unsaturated polyesters contain proportions of propanediol-T. 2 ( S ~ 1 4.9.9) * butanediol-1.3 (ei 's 13.76), pentanediol-1 .5 (cS "= 1 k . 36) , Hsxandi.ol» (S = 12.81), 2-methyl - Pentanediol 1.3 (cT = 1 2. 30), 2 ~ ethyl:,: andio 3. 1.3, 2-ethyl »3-methyl-1 ^J entanediol-1.3 (S- 12.00) or TricyclodccciKlinethanol alü äthergruppcni ' Roic diols, also diethylene glycol (S "Ik,? - h), triethylene glycol, dipropylene glycol]. (S ■■■ 11.53 )?

40984 7/100 8 BAD ORIGINAt

2324Ü61

- 5 - ο.ζ, 2γ14

May 11, 1973

Ti-propylene glycol or doubly ethoxylated or propoxylated Bisphenol A as diols containing ether groups.

In order to obtain polyester molding compounds with a reduced shrinkage compared to the prior art, the diol content of the unsaturated polyester must consist of such a weight ratio of ethylene glycol and a diol with a solubility parameter of 10-15 that the mean solubility parameter is between 15 * 1 and 16.7, where the upper limit depends on the proportion of CK ,, ßunsaturated dicarboxylic acid in the sum of all carboxylic acids. The upper limit is 16.7 with 50-80 mol- ^ o or 16.3 with 80-90 mol- # or finally 16 with 90-100 mol- JO OL, ß-unsaturated carboxylic acid in the acid component of the polyester.

The selected range of the solubility parameter is thereby characterizes that the unsaturated polyester 1. on the one hand good are compatible with the vinyl monomers, on the other hand accordingly the objective result in hot-curing molding compounds that cure without shrinkage or with expansion. Is the mean solubility parameter of diols smaller than 15 · 1 »do not harden. The molding compounds do not non-shrink; becomes the upper critical limit of the mean solubility parameter exceeded, the unsaturated polyester 1. generally incompatible with the vinyl monomers.

Suitable combinations according to the invention consist of 1 mole of fumaric acid, 1 mole of phthalic acid (50 Μο1- ° / ο fumaric acid in the carboxylic acid portion), I.05 mol of glycol and I.05 mol of diethylene glycol. The diols have a weight ratio of 37 ° / ° to 63 ° / o and have an average solubility parameter of 15 · 3 ·

Another suitable combination consists of 1 mol of fumaric acid, 1 mol of phthalic acid, 1.9 mol of glycol and 0.2 mol of diethylene glycol. The diols are in a weight ratio of 85 ^c / o to 15 ψ and have an average solubility parameter of 16.64,

409847/1008

2324U61

- 6 - OZ 2714

May 11, 1973

Particularly suitable are polyesters with a proportion of 65-80 mol% of fumaric acid or maleic acid in the carboxylic acid portion, for example polyester made from 2 mol of fumaric acid, 1 mol of phthalic acid, 2.5 mol of glycol and 0.5 mol of dipropanediol. The diols are in a weight ratio of 70: 30 ° -a and have an average solubility parameter of 15 »3> a polyester made from 3 moles of maleic acid, 1 mole of phthalic acid, 3.2 moles of glycol and 0.8 moles of 1,2-propanediol is also particularly suitable. These diols are in a weight ratio of 76.5: 23.5 and have an average solubility parameter of 16.55 »

Another well-suited Polyestex * consists of 1 mol (= 100 Mol-ji) fumaric acid, O.7 mol of glycol and 0.7 mol of diethylene glycol; here the diols are in a weight ratio of 57.4 and 42.6 txnd have an average solubility parameter of 15 * 84.

The unsaturated polyesters are produced by customary azeotrope or melt condensation of the components at temperatures from 150 to about 250 C. In general, the diols in one about 2 to about 10 percent molar excess over the dicarboxylic acids used. When using the polyester resins together with mineral fillers containing magnesium oxide for Preimpregnating fiberglass mats can be useful to that Use diols and dicarboxylic acids in an equimolecular ratio. However, the molar ratio of the diols and dicarboxylic acids is not critical. The acid numbers of the unsaturated polyesters are in generally between 10 and 70, preferably 20-50, in particular at 25 - 40. Accordingly, the molecular weight is which is not critical to the invention, between 5500 and 800, preferably between 300 and 1000, in particular between 2500 and 1500,

As unsaturated polymerizable vinyl monomers 2. are suitable the usual, such as styrene, substituted styrenes such as tert-butylstyrene or <X-methylstyrene, especially mixtures of the latter

409847/1008

- 7 - ο.ζ. 271 * »■

May 11, 1973

with styrene. Other ethylenically unsaturated monomers that can be used in combination with styrene in amounts of less than 50 percent by weight are lower (C ₁ -C.) - Alkyl esters of acrylic acid or methacrylic acid, and halogenated styrenes vie chlorostyrene or dichlorostyrene, and also atich diallyl phthalate .

The polystyrene used is predominantly commercially available homopolystyrene produced by free radical polymerisation with a K ex ^ t of kO - 100, preferably 50 - 80. It is added to the polyester resin as a 20-50% solution in styrene before curing, before or after the addition of inhibitors, mineral fillers or glass fibers. The polystyrene is 1 to 25 percent by weight, preferably 5 ^ As 20 Percentage by weight, based on the sum of components 1 and 2, contained in the polyester foxromasses.

The ratio of the components -

1. Unsaturated polyester resin

2. Copolymerizable Viriyl Monomer

3. polystyrene

In the three-component system according to the invention, depending on the application and the requirements, the unsaturated polyester 1. can be present in proportions of 20-80 percent by weight, preferably 25-60 percent by weight, in particular 30-50 percent by weight, based on the three-component system. The vinyl monomers can be present in proportions of 20-80 percent by weight, preferably 30-75 percent by weight, in particular k0-60 percent by weight. The polystyrene can be present in amounts of 1-25 percent by weight. Preference is given to using 5 to 20 percent by weight, and more preferably 10 to 15 percent by weight.

409847/1008
BATH ORIGINAL

- 8 - Q.ζ. 2714

May 11, 1973

A particularly suitable mixture consists of

39 percent by weight of a polyester hS percent by weight styrene and 12 percent by weight polystyrene.

The molding compositions according to the invention are in the presence of catalysts, which deliver free radicals quickly enough above approx. 80 C, hardened in the usual way. As such hardening catalysts Benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate are suitable, tert-butyl peroctoate, also dicumyl peroxide, di-tert-butyl peroxide, Cumene hydroperoxide, tert-butyl hydroperoxide or azodiisobutyric acid dinitrile. The amount of hardness catalysts is 0.5 - 5 percent by weight. It is also possible to add hardening accelerators, e.g. tertiary aromatic Amines for combination with diacyl peroxides or cobalt salts for combination with hydro- or ketone peroxides. In the application In this combination, the molding or coating compound must reach a curing temperature of over 80.degree. The polyester molding compounds also contain customary polymerization inhibitors, for example hydroquinone, tert-butylcatechol, benzoquinone, di-tert-butylbenzoquinone and the like, generally about 0.001 to about 0.1 weight percent.

The low-shrink molding compositions according to the invention can be produced by customary Hot pressing process in wet pressing technology, but especially for processing be used as pre-impregnated resin mats (prepregs) or molding compounds.

Xn the wet press ο chnilc fiberglass mats - if necessary, too. GlasfasersträngG (rovings) or fabric, which are made by so-called preform binders can be preformed into the desired shape, in the mold with the catalytic polyester molding overgossesi and by heating also approx. 80 - 170 C, especially 110 - 130 C in

409847/1008

- 9 - O .Z. 2714

May 11, 1973

hardened in the closed form. The polyester molding compounds can with "dex" Maßga.be that the liquid, pourable consistency is preserved remains, mineral fillers such as chalk, kaolin, asbestos flour, talc, kieselguhr, quartz flour, silicon dioxide, and pigments such as titanium dioxide.

The reinforcement fiber content in this case is 5 6O ^c / o, based on the cured molding. When processing as pre-impregnated resin mats (prepregs) or molding compounds, the liquid resins are mixed with polymerization initiators, inert mineral fillers, dyes and lubricants and thickeners such as magnesium oxide, calcium oxide, mixtures of magnesium oxide and calcium oxide, and also zinc oxide, barium oxide, magnesium hydroxide or calcium hydroxide. Mat-like glass fiber materials or cut glass fibers can be impregnated with the still liquid mass. During a ripening period of a few days, the impregnated mats thicken to a non-sticky, storable consistency. The dry, dough-like masses can be hardened by pressing at 100 - 170 C and 50 to 150 kg / cm while shaping. .The thickening agents are used in amounts of 0.2 to about 10 preferably from 0.5 fo _t his 2 weight percent, based on the weight of the unsaturated polyester used. The composition of the pre-impregnated compositions is generally 20-60 parts by weight of polyester molding composition from 1. +2. +3., 20-60 parts by weight of fillers and 5 - kO parts by weight of reinforcing fibers.

The novel molding materials are characterized in that £; ie by hot pressing either shrinking or expansion of up to 5 ^c / j, often even lower than expansion up to 8 ^c / o echoed. Molded parts made from the molding compound have an outstandingly glossy, smooth surface without showing the glass fiber structure. The hardened molded parts are microscopically heterogeneous, ie two-phase structures made of hardened polyester

409847/1008

May 11, 1973

Resin with spherical polystyrene inclusions, but macroscopic completely homogeneous, i.e. the surfaces and fracture surfaces show a uniform white color.

It was not foreseeable that by simple measures - namely by using a certain content of C6, ß-unsaturated dicarboxylic acids in connection with easily accessible diols in the proportions according to the invention, such a technical advance could be achieved. It is known from the literature (Kunststoff-Adviser 10, 1970, page 963) that it is extremely difficult to find a suitable thermoplastic for a particular polyester resin. This difficulty is due to the processes involved in hardening, which have not yet been fully clarified.

Examples

Polyester resins are produced from the components listed in Tables 1-3. For example, the polyester according to Example 1 is produced as follows: 348 parts of fumaric acid, hkk parts of phthalic acid, 195 parts of glycol and 333 parts of diglycol, the molar ratio of these components is 1 s 1: 1.05! I.05 are esterified while passing through a stream of nitrogen at 195-200 ° C. until the acid number is 32 mg KOH / g substance.

The polyester obtained is mixed after the addition of 0.165 g = 0.01 ° / o hydroquinone in the ratio 65 1 35 with styrene, forming a clear homogeneous solution. The other polyesters listed in Table 1-3 are produced in the same way, mixed with styrene and assessed for appearance.

It is also a solution of a commercially available polystyrene. (VESTYRON® 121) with a K value of 6k in styrene, the mixing ratio of polystyrene: styrene being 30:70. The solution is ^{stabilized with 0.01 c} / o hydroquinone.

409847/1008

- 11 - OZ 271 ^

May 11, 1973

In each case 6θ parts of the polyester / styrene solution and 6θ parts of the polyctyrene / styrene solution are mixed intensively, an opaque dispersion being formed. The mixing ratio of the 3 components is:

Polyester: 39 percent by weight, styrene: 49 percent by weight Polystyrene: 12 percent by weight

50 S of this mixture with 25 g Quarzinehl and 0.5 g of dibenzoyl peroxide paste (50prozentig in plasticizer) are each stirred for curing. One half of this molding compound is cured at 95 ° C. for 15 minutes, while the second half is retained to determine the density of the uncured molding compound (see formula). The density of the hardened and uncured molding compound is measured. Axis of the measurement data, the shrinkage is calculated according to the following equation:

Density of the hardened molding compound - density of the

"," _R / unge tempering eten molding material., _Λ _

Shrinkage ^c / o = ■■■ - · 100

⁰ density of the uncured molding compound

Positive numerical values therefore mean shrinkage, negative numerical values mean expansion upon hardening. The data are summarized in Table 1-4.

In the examples and comparative examples, groups of Polyesters with the same fumaric acid: phthalic acid ratio combined.

The comparative examples A - L show that numerous polyester resins, including commercial sales products, not those according to the invention Show effect, and that at the transition from the mean solubility »parameter from 15.0 to over 15 · 3 surprisingly a_ erratic

Change of the skip values from positive to negative "fourth takes place.

409847/1008

- 12 - OZ 2714

11.5 *. 1973

Comparative Examples I-L show the upper limit of the solubility parameters from 4/16 - 8/16, which is characterized by non-contractual lce.it the polyester with styrene.

Comparative Examples M - H show that the erfindungsgemäßο effect in the known cold curing of polyester resins with the addition of Polyst} ^r rol can not be achieved. Comparative experiment S proves that the known addition of solid, powdery polystyrene does not allow shrinkage-free curing polyester shapes to be obtained.

409847/1008 ORIGINAL BATHROOM

O.Z.

May 11, 1973

U MH CA τ— Ο 1.0 τ— CA τ— 6.2 2.8 τ— O »Λ
τ- τ— O τ— I. I. ⁺ IA ⁺ »Λ ^{1 +} + + ti £> U . φ Η cd t— τ— τ- CM Cv! CM ^) U U U U U U H Φ ρ !, ϊ + ~ * CD CD CD CD CD CD CD . Cj CD W OCM H H H H H H H H H IQ U -P τ- Ai m O Ai Ai Ai [V ₁ ^ Φ (Q © <'ö Φ Ν CA CA CO CO CA {Q · C - \ j v / 0 “A r- CM
r— τ— r- τ— CA
t ™ " CA CA r ^ i Ci I H Cl HO> -PO ₁ S, 0) 3 -rl ¹ -Uj cq -ϋ - ' -XI φ ι — r ΙΛΟ H ~ tR ΙΛΟ ΙΛΟ CM O ^ Hr— (I O O CM O VC YES IA CA 1ΛΌ φ. * · '· • · «. . * -P Ai ο £ τ- CA τ- CA O τ- τ- CO τ— τ— : cd i >> S ι G) VO VO CA ΙΛ • H H'-Jrj>.
P i50 - ' -XI cd ~ ϊ £. ft ι — ι ι mo ΙΛΟ O H CM Ο \ Ά O t> CM IA-C " fc HO £ • * * · • * • * P * o.S. © τ- CA O O O!> r- CO • H -H ¹ -te, VO CA VO P Ό ^! - ' ILO
tO ΙΛΟ ΙΛΟ p,, -j, -j. OO> Λ CM τ- τ- O IAC- CM CO O 0 0 £ . · • * • «■> . U "H ₁ Sj Φ τ- OO T-VO CAO Γ— τ— CM CM νο CA O
t— VO I.
Φ H ^ ΙΛΟ ΙΛΟ HO, -, I. O O CM O ΙΛΟ g% ο> T ^ £ - CM O -PH ₁ Si Φ CA : <! fco —'O, H cd οι — ι AU H +5 _3 ^ o τ— τ— S ffil ^ J k c;, - t IA cd U H * E p O CM CM jj ^ {qI-I P. ω • Η U CM CA P. ο & m

409847/1008

Tabel

Ex.
No. Fumar
acid
QvfolJ Phthal
acid
[Mole] Ethylene
glycol
[Mole]
[Ge-w .-? £] Propane-
diol
[Mole]
[Gew.-JoJ Dipropane
diol
_ Γ ^Μοΐ 1
JGev.-5-Γ] Diethylene
glycol
[Mole]
[Ge-W .- $] Butane-
diol-1.3
JMoli
[Ge-W .- $ [[ SD Appearance
the poly-
esterhar-
ze ² I Shrink
fung 3 1
fol-fo] «Α
•
JT
• 4th 1 - 0.52
37.00 Ο.52
63.ΟΟ 15.3 clear - 3.5 973 G 1 - 1.05
100.00 14.99 clear ₊ 3.6 H '2 - 1.05
36.20 1.05
63.80 12.79 clear + 3.0 5 1 0.7
57.4 0.3
42.6 15 · 8 clear - 6.4 6th 2 - 1.4
57.6 0.6
42.4 15.8 easy
cloudy - 8.9 T 1 0.9
85.00 0.1
3 p.m. 16.4 crystal
lin Ml 7th 3 1 3.6
84.2 0.4
14.8 16.45 clear - 5.3 8th 3 1 3.2
76.5 0.8
23.5 16.55 clear K 3 1 3.6
88.2 0.4
11 .8 16.8 2 layers
th -

OZ 2714 "Ϊ May 1, 1973

co Ε- ·

> o CM VO r- ■ CM T— • T- T— I. τ— CM t— VO CM o ~ t— f )O fa fiO H
A ti O CM cn + ₊ VO ₊ P-, υ a> ι I. I. I. I. ₊ CQ Ch 1 I. CM S —N ΐ— A. r— CM O H (d -it- * S ο ti U ^^ _t ^ U ^ ο ί! U U X— H • A O CD Ό CD "O U CD Θ Pll if * CD CD O a CD Ci A · Ρ ti H H CD H O) OCM H H H H O \> Αί H (Q U -P A4 A4 Ai ω Ah 3 ο ω ο <j -Ö Φ Ν CM CM VO
cn | L / c) vo · VO VO vo •
T— t— "O
"O VO cn VO VO VO
t— VO Vd cd H jo cn co * » 3 -ri ¹ ^ Φ ο cn η τι, c5j ά Φ I — Γ t - I - fjp ^ ^ H H I il ο ο cno CM CO CM τ- • · • · * · : ri "£ ■. Φ OVO O IO O 1Λ r— γ- r ™ ά ι — ι
cd ι — teS. P ₄ HI O O in H ι JiJ ι Is p, _O l -I φ • ri -ri, Ü, η ό '- ³ «^? 1OO IOO cd τ-tT r- O T- O CM -3 " p .: H H • · OO IO • « OOO £ cno cno T— ^ j- O
T— O
t— ο cn cn Cl "^ i.
O Hj rl
HOH '· O O CM ca ve (*> r * 4 O IS t-CM * « ΟΟ cn C \ O CM O CJ ok CM JO , ti t'nl ^ J ^ ¹ CMVO CM ^ f τ— _ ^ - t - IO O cn ¹ Xj -i ^J H '| O ι CO OO OO OO r— : <ta · - ' I. CtJ O! 1 AU H -P ^ i O Τ— P, « ^l - ' I. Ci Jh ¹ H ¹ P P P. cn C. cn Ci ". ' ♦ .-— * • ri ^ in O

409847 / Ί 008

Tab 1 1 e

JJGXSp.
No. * Fumar
acid
j}! ο l] Phthal
acid
[Mole} Ethylene
glycol
pioi] Propane-
diol
ImoiI
pew.-16] Dipropane
diol
fc f ^l0l ] -i
^ ew .-% J Diethylene
glycol
r & ^ol 3n
jGew.-5 & J Butane-
diol-1.3
rl? ^Iol Ji
| Weight-50 Sd Appearance
the poly-
esterhar-
ze 2) Shrink
fung ³ ^
JVol -? (] 3 1 2.4
55.0 1.6
45.0 16.12 clear + 1. O ^ S ⁶ > 2 1 3.15
100.00 14.99 clear + 3.5%

- 17 - OZ 2714

May 11, 1973

to the tables

1) mean solubility parameters, calculated according to S = 17 * 2 (Weight percent glycol) + «S ^. _ (Weight percent diol)

2) after ? Λ hours

3) Unless otherwise stated, after curing at 90 ° C

k) Mixtures of 70 percent by weight polyester and 30 percent by weight styrene (in all other examples 35 ^o i <> styrene)

.5) The comparative experiments were carried out at room temperature (20 c) by adding 0.5 S dibenzoyl peroxide and 0.05 ml of a 10 percent strength methylaniline solution to 75 S of a mixture of 30 g styrene-containing polyester resin (35 ° / ° styrene), 20 g of a 30 percent strength polystyrene solution hardened in styrene and 25 S quartz powder.

6) The Comparative Experiment S was prepared by curing of 75 g of a mixture of hh g polyester resin with a styrene content of 55.7 / 3 »6 g of solid, powdered polystyrene having a K ¥ ert of 6h and an average grain diameter of 0.7 mm and 25 S silica flour carried out with O.5 S benzoyl peroxide at 95 C. The quantitative ratio is the same as in experiment M.

409847/1008

Claims (1)

Claims 4. an activator system, which starts above 80 C. and 5. customary auxiliaries and additives, such as Inhibitors, mineral fillers or glass fibers, characterized in that the unsaturated polyester 1. a condensation product is off A. one or more dicarboxylic acids, with at least 50 Mol percent of the acids C £, ß-unsaturated dicarboxylic acids are and B. a mixture of I. ethylene glycol and II. Diols with a solubility parameter from 10 to 15 » where the mean solubility parameter of the mixture of I * and II. - on the basis of the weight fractions of the glycols - between 15.1 and 16.7. 2. Heat-curing polyester molding composition according to claim 1, characterized in that the unsaturated polyester 1. in the acid component 50 to 80 Mole percent QS-, ß-unsaturated acids and diols I. and II., whose mean solubility parameter is between I5 «1 and I6.7., 409847/1008 - 19 - OZ 271 ** 11.5.19.73 3. Heat-curing polyester molding compound according to claim 1,
characterized in that the unsaturated polyester 1. in the acid component 80 to 90
Mol percent of ct., Ss-unsaturated acids and diols I. and II., The mean solubility parameter of which is between 15.1 and 16.3. k, heat-curing polyester molding compound according to claim 1,
characterized in that the unsaturated polyester 1. in the acid component 90 to 100 Molar percent 06, ß-unsaturated acids and diols I. and II. Contains, the mean solubility parameter of which is between 15.1 and 16.0. 409 847/1008