DE2548292A1 - HYDROXYBENZENE AS PROMOTORS FOR THE (CO) POLYMERIZATION OF UNSATURATED POLYESTER RESINS - Google Patents

Description

The present invention relates to a method of manufacture polymerizable or copolymerizable mixtures, which are composed of an unsaturated polyester or a mixture of such a polyester and one copolymerizable therewith Monomers / a ketone peroxide as an initiator / a metal compound as an accelerator and a promoter, furthermore the polymerisation or copolymerisation of such mixtures and further moldings / which are wholly or largely consist of the above-mentioned poly- or copolymers.

Unsaturated polyesters can be made about equivalent by reaction Amounts of a polyhydric alcohol such as ethylene glycol / diethylene glycol, Triethylene glycol, trimethylene glycol, propylene glycol, Pentaerythritol or another diol or polyol with an unsaturated dibasic carboxylic acid or a dicarboxylic acid cynhydride such as maleic acid, maleic anhydride, fumaric acid, itaconic acid or citraconic acid. These unsaturated Dibasic carboxylic acids or anhydrides are often used together with aromatic and / or saturated dicarboxylic acids or their anhydrides such as phthalic acid, phthalic anhydride, isophthalic acid, tetrachlorophthalic acid, malonic acid, adipic acid, Sebacic acid, tartaric acid etc. are used.

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Unsaturated polyesters containing vinyl or vinylidene groups can be obtained by polycondensation of cL _t $ -unsaturated monocarboxylic acids such as acrylic acid or methacrylic acid with mono-, di- or polyhydroxy compounds. Examples of hydroxy compounds that may be mentioned are: methanol, ethanol. Isopropanol; Cyclohexanol, phenol, ethylene glycol, propylene glycol, 2,2-bis- (4-hydroxyphenyl) -propane, 2.2-bis- (4-hydroxycyclohexyl) -propane, 2.2-bis- (4-ß-hydroxyäthyloxyphenyl) -propane, pentaerythritol and the dimer of the same, trimethylolpropane and glycerol and those in NL-OS 6 808 040, DT-PS. 1,645,379, US-PS 2,895,950, US-PS 2,628,178, <3B-PS 928 307, GB-PS 965 826 and FR-PS 1 404.

Unsaturated polyesters containing vinyl and vinylidene groups can also be achieved by reacting ol, ji -unsaturated monocarboxylic acids with compounds containing epoxy groups such as bisphenol A diglycidether.

The unsaturated polyesters described above can be dissolved in monomers which are copolymerizable with the polyester and have one or more CH ₂ = C ^ groups, for example in styrene, vinyl toluene, methyl methacrylate. or ethylene glycol dimethacrylate. Usually solutions are used which contain 70-50% by weight of the unsaturated polyester and 30-50% by weight of the copolymerizable monomer. Styrene is preferred as the copolymerizable monomer.

In order to improve the stability, the unsaturated Polyester inhibitors incorporated, in amounts of 0.001 to 0.03 wt .-%. The most common inhibitors are hydroquinone, Quinone and p-tert-butyl catechol.

The unsaturated polyesters described above or their Mixtures, rii t copolymerizable monomers can under the

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Inachqereicht j

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Action of initiators, these are known to be compounds, which generate free radicals, polymerized or copolymerized will. Ketone peroxides are preferably used as initiators. If the polymerization or copolymerization at If it is to be carried out at room temperature, it is advisable to use an accelerator for the peroxide in addition to the ketone peroxide apply. Metal compounds are often used as such.

The present invention relates to a method of production a polymerizable or copolymerizable mixture consisting of an unsaturated polyester or the Mixture of an unsaturated polyester and a monomer copolymerizable therewith, a ketone peroxide as initiator and a metal compound as an accelerator, which is characterized in that one or more hydroxyl compounds are added to the mixture the formula

OR,

in which R stands for hydrogen or a lower alkyl group, added.

As has been found, surprisingly, have those according to the invention Processes obtainable products have a greater hardness than those products which are produced without the addition of the above-mentioned hydroxyl compound were manufactured. It was also found that by varying the amount of the hydroxyl compound added Gel time can be adapted to the different conditions given in practice.

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Examples of the hydroxy compounds to be used according to the invention are resorcinol (R = H) , 3-methoxyphenol (R = CH ^) and 3-octyloxyphenol

The amount of promoter to be added according to the invention depends the polymer or copolymer to be produced from / siö can be varied within wide limits. Preferably the hydroxyl compound is used in amounts from 0.01 to 2.0 Percentage by weight, based on the polyester or the polyester / monomer mixture applied.

Example? »For the polymerization according to the invention or Ketone peroxides to be used for copolymerization are methyl ethyl ketone peroxide, Methyl isobutyl ketone peroxide, acetyl acetone peroxide and cyclohexanone peroxide. You can ..n amounts of 0/05 to 5.0 percent by weight, based on poly or copolyester, be applied.

The present invention also relates to obtainable by the process described above - polymerizable or copolymerizable mixtures consisting of an unsaturated one Polyester or the mixture of an unsaturated polyester and a monomer copolymerizable therewith, a Ketone peroxide as an initiator, a metal compound as an accelerator and a hydroxyl compound of the formula given above. Mixtures which contain the hydroxyl compound are preferred in an amount of 0.01 to 2.0 percent by weight, based on the polyester or on the polyester / monomer mixture contain.

The invention also relates to a method of polymerization or copolymerization of an unsaturated polyester; or ic-iner mixture of a polyester and a herewith

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CHI-j

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copolymerizable monomers. The process is characterized in that the mixture described above is polymerized or copolymerized ^{at temperatures from 0 to 50 ° C.} The poly- or copolymerization is preferably carried out at room temperature and in the presence of a cobalt, iron / copper, vanadium or manganese compound. Preferred metal compounds are cobalt naphtenate, cobalt 2-ethylhexanoate and cobalt stearate. These cobalt compounds are used in amounts of 0.001 to 0.5 percent by weight, preferably in amounts of 0.005 to 0.05 percent by weight, based on the poly- or copolyester.

Another object of the invention are moldings that consist entirely or predominantly of a polymer or copolymer obtainable by the process described above.

The invention is further illustrated by the following embodiments: The Geller tent was determined at 20 ⁰ C. The hardness was determined at room temperature using a Persoz hardness tester on 1 mm thick layers of the unsaturated polyester. During the curing, the layer was covered with a tin foil in order to prevent the evaporation of the monomer and / or an inhibition by atmospheric oxygen if necessary.

The measurements were carried out on the following samples:

H ar % : A; Reaction product of 1.0 mol of maleic anhydride, 1.0 mol of phthalic anhydride, 1.1 mol of ethylene glycol and 1.1 mol of propane-1,2-diol, added with styrene up to a styrene content of 35 %.

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Resin B; Reaction product of 2 moles of bisphenol A diglycidabher and 2 moles of methyl methacrylate, mixed with styrene up to a styrene content of 45%.

example 1

100 parts by weight of resin A were admixed with one part by weight of a solution of cobalt naphtenate in dimethyl phthalate containing one percent by weight of cobalt, one part by weight of methyl ethyl ketone peroxide with an active oxygen content (AO) of 9.2% and 0.55 parts by weight of resorcinol. Gelierze.it was measured on the mixture obtained at 20 ° C. and Persoz hardness after 2, 6 and 24 hours. The same measurements were carried out on mixtures containing no resorcinol or 0.07, 0.14 or 0.28 percent by weight resorcinol. In addition, the measurements were carried out on mixtures containing 2.0 parts weighting- te Möthyläthylketon peroxide contained.

The composition of the mixture, the gel times and the measured Peraoz hardness clay are shown in Table I.

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6Π9820 / 0993

vo CN IP

CN Q O η

OJ H

Γ> Q) 1 KJ

rH CN ι O CN -r » in in rH ! α si rH C) m rH CO ■ D O d Xl rH rH Tj ■! J •he rH CN rH Ci 4) r; in ro rH ; "j • rH -H -H VO cn I J) O Ή •H CO co M. rH CN . ~ * CS CN ) η ν ^Λ 1 U
; ■ - 'Tj • rH ■ ι υ O O\ "-1 -I O ,1 Crt - ~ Ί I in . OJ O r-i rH ■) rH CN - '\ O in (.1 • MM # "** • «3 · Crt O ί> O tn O rH CN . ·. ', ι * i CTi rH CN I. co CN CN VO O VO J ^ rH rH rH H O C7> Γ- « OJ rA rH ■ VO O CTl f I r- \ rH rH CO co O ■ .T » • rH ■ sr H f- O r-1 H co rH H CN CN ro CU • rH Oil CO O •so rH rH IT) rH i-H m a <n CN VO rH O CO O rH rH CN i VO r- r-i CO U r-- .-I Ü ti ■ ri O) ? "9, ϋ ■ f j * * rH Jl 'J -; .u fi "6 'V " i) α r. Oil n _; '"1 r: j pi
1 ei / ■; , -} -IJ -I : ι 0 I J r! π ■ <■] 01 ; . ■■ Ü) , Ct . ) r < r 'I : l "6 I '''i '-! ο O rH ο ο rH Q Q rH ο ο ο ο r-i O O rH O O rH O O rH O O rH O O rH ft ¹ t-1 id l.-l

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j i.iACH '..-; r. ^; .ri.i »*> H

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Example 2

100 parts by weight of the resin Λ were with one part by weight of a solution of cobalt 2-ethylhexanoate in dimethyl phthalate, which contained one percent by weight of cobalt, one part by weight of acetyl acetone peroxide with an active oxygen content of 0.4% and 0.07 parts by weight of resorcinol are added. At the received The mixture measured the gel time at 20 ° C. and the persistence after 2.6 and 24 hours. The same Measurements were also taken. Mixtures carried out, which no resorcinol, 0.23 percent by weight or resorcinol instead of Resorcinol contained 0.57 percent by weight of 3-octyloxyphenol. In addition, the measurements were carried out on mixtures which, instead of acetylacetone peroxide, methyl ethyl ketone, Cyclohexanone or methylinobutyl ketone peroxide contained.

The composition of the mixtures, the gel times and the The measured Persoz hardnesses are given in Table II below shown.

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l «MW '**

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Table II

5.

m σ

Ears A 100 100 100 100 100 100. 100 100 Cobalt accelerator 1 1 1 ^: 1 1 1 1 : 1 ο 'acetylacetone peroxide
ο (4.0% AO)
CO 1 1 ; 1 ■. 1 -; -: - - 00
Is ₀ methyl ethyl ketone
o peroxide (9.0% AO) - ■ - - ■; - ■ 1 ■ ι: 1 1 O
co cyclohexanone peroxide
co (6.5% AO)
CO - - ■ - ■ - - ■ ' - - - Methvliaobutyiketone
peroxide (10.2% AO) - - -; - - - - Resorcinol - 0.07. 0.28 - - 0.07 0.28 - 3-octyloxyphenol - - - 0.57 - - 0.57 Geiiarsait at 20 ⁰ C (min) 15th 17th 17th 14th 15th 18th 16 14th Peraoz hardness after 2 hours
Il Il Il g II
Il Il 24 " 73
127
169 73
139
190 89
156
213 107
150
205 33
80
136 35
98
162. ■ 49
120
190 39
107
169

- Io -

cn

OO <p

ro

Table II continued - Io -

A3CD21626

O CO OO

FS) O

-v,

O CO CO CO

CO
13th

Kara A | loo! I. 100 - 100 i 4 δ loo ji loo!
ti i 1 j
ί 100 ! 100 100 j 1 Cobalt accelerator 1 1 0.07 1 \ 37
118
192 ι! !
! ^λ 1 I ³⁴ 1 1 J-
9 Acecylacetone peroxide
(4.0 % AO) "j
S. I.
J " (
j ~ - - ! ~ 30th
84
166 - - - Methyl ethyl ketone peroscid
(9.0 * S AO) - 50
• t ι ι
ϊ
\
j - 0.57 Cy c i-2 *;: snoii-per oxide
(6.5 δ AO) I 27
68
132
ti ¹ 30th
94
1S9 1 I ⁴⁷ 30th Methviisobutyl ketone peroxide
(10.2 S AO) - "~ i I.
I 59
i 1 ¹ 31
95
173 Resorcinol 0.28 - ι
ί 0.07
¹ 0.28 3-Glyoxy-phenol I 0.57 j ' Gaiieraeir. up to 20 ° G (rriin) 26 y 23 PerEO ^ hardness after 2 hours
f! «Ii C * Il
"" w 24 " 55
112
177 32
105
189
i

-ο

CO

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ICO weight point of resin B was added with one part by weight of the cobalt-containing accelerator described in Example 1, one part by weight of acetylacetone peroxide with an active oxygen content of 4.0% and 0.07 parts by weight of resorcinol. The gel time at 20 ⁰ C and the Persoz IIärto after 2, 6 and 24 hours vmrden of the resulting mixture determined.

The same measurements are carried out on mixtures contained no resorcinol or 0.28 percent by weight resorcinol. In addition, the measurements were also carried out on mixtures containing methyl ethyl ketone, Cyclohexanone or methyl isobutyl ketone peroxide.

The composition of the mixtures as well as the measured Golfing times and persons are given in Table III shown.

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iNSPECTEO

..1

VO CN να rH (N

H H I. H CN Φ r-i H I. Φ

approx

H ¹ T) ι ! I. i I. I. H CN CN Φ <Λ ιη as ο • Η a Ci • tn Ι * · CTt cr> VO ο ο O O O 1 * 1 r-H CN r-l H O I. +) I. Ci I. -P rH O co : ro ΙΛ ^ O M. φ φ in ΐ ^τ 1 ιη Γ- VO O Φ M. X O I. r-H CN rH rH Oil I. I. O I. rH <7 \ M. 1 ιη CO C; > 1 I. H
rH O ιη a \
rH O
rH a O + J co V) H ο I. -! J I. r-i H I. IN ro U ι VO O -P : < ^T i Ü 4th in Φ rH H O (U r-i S = i O O Ρ « H (N H rH ο I. > l I. U r-l (Q I. O I. ΓΛ O O -f ^! -H CO O O rH ■ -Η I. rH Ή I. d CN H Π) I. I. I. J I. O
O • Ρ SI Xi - ■ H 4_) co H υ I. H I. (U I. CN 00 O χί SÜ in I. r- O d H CN O
rH rH I. r-l I. I. Γ-
O O r-i m- O in I. in O d rH CN H I. H I. \ ' O O in ο ι CO ί CM O O H CN r-i 00 , _! H I. I. I. CS VO UV O • O } I. O O O (N CN H rH H I. I. I. O r-i • Η O * O I. I. CN O O m H • Η I. t I. O ¹ H I. 1 O in) M. S. φ U O O O ■ Η q «J O d dP CN Φ do H in (N •H CJ O • Φ φ O « O τί 03 rH γ: K CJ O +1 PQ OJ ■ r) ■ -μ TJ rrj ^r C! Φ • rl •H -rH -H H .H Ά υ M. CN VO ti ¹ Ki O 0 O C) U Φ (N .Q * J ^ i-l O • Η ^! N O 'J) Θ φ 05 .H O M. <"l) Φ «3 S. IiJ O f4

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Claims (6)

Patent claims: I) / Process for the preparation of a polymerizable or copolymerizable mixture consisting of an unsaturated polyester or a mixture of an unsaturated one Polyester and a monomer copolymerizable with it / a ketone peroxide as initiator and a metal compound as accelerator, characterized in that one of the Mixture of one or more hydroxy compounds of the formula OR, in which R stands for hydrogen or a lower alkyl group, added. 2) Method according to claim 1, characterized in that the hydroxyl compound in amounts of 0.01 to 2.0 percent by weight, based on the polyester or avf, the polyester / monomer mixture is used. 3) consisting of polymerizable or copolymerizable mixture made of an unsaturated polyester or a mixture of one unsaturated polyester and a monomer copolymerizable therewith, a ketone peroxide as initiator, a Metal compound as an accelerator and a hydroxyl compound the formula 609820/0993 ~ ¹⁴ 2 5 48 2 97 "] - 14 - A3CD21626 in which R stands for hydrogen or a lower alkyl group, 4) Mixture according to claim 3 / characterized in that / 3 they the hydroxyl compound in an amount from 0.01 to 2.0 Percentage by weight, based on the polyester or on the polyester / monomer mixture. 5) A process for the polymerization or copolymerization of an unsaturated polyester or a mixture of a polyester and a monomer copolymerizable therewith, characterized in that the mixture according to dan claims 3 and 4 at Temj
copolymerized. 3 and 4 polymerized or at temperatures of 0 to 50 C 6) molded body, characterized in that it consists entirely or predominantly of a by the method according to claim 5 available polymer or copolymer exist. 609820/0993