DE1669751A1 - Preparations which can be set with water - Google Patents

Description

The present invention "relates to water settables ("water-setable") preparations made from unsaturated polyesters and inorganic, hydraulic fillers with improved service life «,

Preparations made from unsaturated polyesters and bindable with water inorganic hydraulic fillers are described in British Patent 1,065,053

The term "service life" means in the present application the time between adding water to setting the Frühfjarates and the time when the preparations for stirring and Applying too thick. For most uses it is a relatively long life is advisable in order to (a) thoroughly mix the preparation with that used to set the material Water and with any inert fillers and additives that one wishes to add, (b) the transport of the Mixing from the mixer to the point of use and its application by hand trowels etc. or by mechanical application devices, and (c) removing excess mixture after

909820/1288

. ■ - ■■ .- "■ V" - 2 ■ '■ ■ ■ .- ■■.. ^"':

the application from the mixer and the application tools or machines to enable. ...

The aim of the present invention is to create water-settable preparations made from polyesters and inorganic, hydraulic ones Fillers with an improved service life.

The _? Water-settable preparations made from polyesters and inorganic, hydraulic fillers include a polymerizable, unsaturated polyester, an ethylenically unsaturated monomer which is copolymerizable with this polyester, an inorganic, hydraulic filler which, when mixed with water, causes or induces an alkaline reaction and becomes a solid Sets mass, a water-soluble polymerization initiator, which does not initiate polymerization of the unsaturated monomers and polyester in the substantial absence of water. - »e-iocn u.-v-er aqueous alkaline conditions becomes active, and 0.1-20 wt» - ^ (based on the combined weight of polyester and unsaturated monomer) of a compound with at least one acid or anhydride group and a C ₁ Q-CgQ aliphatic and / or alicyclic group which contains unsaturated bonds which can be oxidized in the air at room temperature, or a salt thereof in which the positive radical does not accelerate the effectiveness of the polymerization initiator.

SAD. ORIGIN ^M

9098 2 0/1288

The unsaturated polyesters are known from the literature and can be obtained by polycondensation of a polycarboxylic acid (or its Anhydride) can be produced with a polyhydric alcohol, one of the components being a non-aromatic, unsaturated one Has a bond that can undergo addition polymerization, e.g., an ethylenically unsaturated bond. Mainly are dicarboxylic acids, especially the eC, ß-unsaturated <jl, ß -dicarboxylic acids, and dihydric alcohols are used. the unsaturated acids can partially be replaced by a saturated ^ Polycarboxylic acid, e.g. phthalic or isophthalic acid. A mixture of saturated and unsaturated dibasic acids is preferably used together with a glycol. Suitable, unsaturated acids are e.g. maleic, fumaric acid or their anhydrides. Suitable dihydric alcohols are 25.B. Ethylene glycol, diethylene glycol, propylene glycol and hexylene glycol. Part of the dihydric alcohol can be replaced by polyhydric alcohol such as Pentaerythritol, or be replaced by monohydric alcohols such as cyclohexanol. Suitable polyesters can also by the alternative method of converting the polycarboxylic acids or fj -anhydrides are produced with alkylene oxides. Suitable alkylene oxides are ethylene oxide> Propylene oxide and butylene oxide.

Suitable ethylenically unsaturated monomers are from the literature known and include monomeric vinyl and substituted vinyl compounds, such as vinyl esters, the esters of acrylic, methacrylic, maleic or eumaric acid, allyl and poly ally! / compounds and aromatic vinyl compounds such as styrene. The monomer can be a

be a monomeric vinyl compound, in which the polyester in normal -

x · way solves ..

909820/1288

..: "; ^ ₄ - - ^-:; The polyester containing a portion ■ - unreacted carboxyl groups in the polymer chain, and these gebenjhä an acid value Particularly suitable polyesters have acid values of 10 to 50 mg potassium hydroxide per gram...

Most expediently, the combined weight of polyester and copolymerizable monomer, based on the total weight of the preparation, is between 5-95%, preferably between 25-85 ° · The weight of the polyester, based on the combined product. weight of polyester and monomers, is expediently between $ 20-80, preferably between $ 50-70. ■

After stirring with water, the inorganic, hydraulic fillers show or induce an alkaline reaction; these Effect is mainly due to the presence of calcium hydroxide caused. Such fillers are e.g. hydraulic mortars, especially cements such as Portland cement, ferro-Portland cement, Blast furnace cement (slag cement), cement with high alumina content (Ciment de la Farge), lime-Pozzolana cement, natural cements that are used in a mixture with quicklime, and also the hydraulic limes and patent cement. Portland cement is preferred; it is obtained by heat treatment a mixture of chalk (or another lime compound) and clay (or other silica compound), however, can contain any inorganic, hydraulic substance (i.e. one those that occur when mixed with water at room temperature under Formation of a crystalline network structure reacts, which has a certain degree of mechanical stability and / or physical Strength shows). The cements can be of any color and

. 9098 20/128 8

preferably become a powder with a surface area from 1,000 to 10,000 cm / g at the time of their incorporation into the preparation. Portland cement that contains a fatty acid like stearic acid, when incorporated into the preparations, provides more stable dispersions than the cement without it Acid. The oleophilic coating of the cement particles also improves

the effectiveness with which the cement becomes when added to the polyester and monomers dispersed.

The weight of the inorganic, hydraulic filler in relation on the total weight of the preparation can be between $ 5-95, preferably between $ 15-75. About 40% by weight of this filler have been found to be the best proportion for virtually all purposes.

The amount of water used to hydrate the inorganic hydraulic filler and initiate the polymerization of the polyester / monomer system is preferably about $ 25, based on the weight of this filler present in the preparation. The minimum water content is expediently about 5 ^a fa, if the water content exceeds 40% by weight, products with lower strength are obtained. The minimum amount depends mainly on the amount of filler in the preparation. A preferred range is about 15-40% by weight Water, based on the filler.

In addition to the inorganic, hydraulic, water-settable filler, an inert, non-hydratable filler can also be present in the preparations according to the invention, for example; Silicic acid, sand, gravel, fine and coarse flint aggregates, ".

SAD 9 0 9 8 2 0/1288

-β - ^:. ■. ■ ■. ■; ■ ■; ■■ '■■■; -

Bauxite and other mineral fillers commonly used in construction commercial and similar fields. This additional = Borrowed fillers should be added to the preparations just before use be admitted.

The water-soluble polymerization initiators generate free radicals Compounds which are practically insoluble in the monomer and / or polyester, but which are produced as a fine dispersion in the monomer and polyesters can be present and are preferably also present in this way. The preferred initiators are effective at pH in the range of 7.5-11. These compounds are rich in Oxygen; the water-soluble salts are particularly suitable of peracids, such as persulfuric acid, especially ammonium, Sodium and potassium persulfate. The free radical forming compounds " bonds can be redox polymerization initiator systems, the on the one hand the oxygen-rich compound and on the other hand Reactants with the same as reducing agents. So the salts of peracids can be used as initiators and Sulphites are used as activators, the two being one Form a redox initiator system, such as "in." Vinyl and Related Polymers "(published by John Wiley, 1952), page 93, Kepitel II. The reducing agents are not critical, and the salts of the peracids can be made in the presence of portland cement act as initiators without adding an activator. Of the Activator can be any suitable, stable reducing agent, such as "e.g. sodium metabisulfite, which is preferred but not the only possible connection is. There can also be other activating agents Materials and / or dryers such as cobalt naphthenate with any other ^ desired, usual additives be present ".

. ... ■ 909820/1288

The water-soluble polymerization initiators should be present in an amount effective to initiate the polymerization. The type of initiator and its usable amounts are known.
Typical amounts are between 0.5-15 wt .- ^, based on the (each total weight of unsaturated polyester resin and thus copolymerizable monomers.

The compound having at least one acid or anhydride group and a C ₁₀ -Cg ₀ aliphatic and / or alicyclic group which contains unsaturated bonds which can be oxidized in air at room temperature, or a salt thereof can be used in an amount between 0.1-20 Wt .- ^, based on the combined weight of polymer and unsaturated monomer, preferably in an amount between $ 0.2-5, be present. The connection must be at
Room temperature, usually ie between 5-25 ⁰ C., and be oxidised in particular between 18-20 C ». ₉ The aliphatic ^ and / or alicyclic group usually contains at least
an ethylenically unsaturated group in which the carbon atom is in the O-position to the carbon atom of the unsaturated group

a hydrogen atom is bonded, i.e. the grouping

»I I

-C = C-C-t

contains.

90 9820/1288

-; ■ :. - - ■■■■ - - _ 8 _ · - - ■■:. ■■ -Usefully, the positive radical of the salt is a metal, examples of suitable metal salts include monovalent salts such as those of the "alkali metals, eg sodium and potassium, polyvalent salts such as those of the alkaline earth metals, for example calcium, and other metals such as zinc or lead. Metals, which accelerate the effectiveness of such polymerization initiators and are therefore unsuitable as positive radicals, are known} the best-known examples include copper and silver.

.Compounds containing such ethylenically unsaturated bonds, are e.g. oleic acid, linoleic acid, linolenic acid, bicinoleic acid, Elaostearic acid, acids derived from fish oils and Dicarboxylic acids with alkene radicals, such as n-dodeceny / succinic acid. Such compounds have a measurable iodine number. Suitable connections have iodine numbers of 10-200 centigrams / g.

The compound can expediently be derived from drying oils and semi-drying oils or from derivatives of these oils. "Drying oils" and "semi-drying oils" are understood to mean vegetable or animal oils and certain other liquid substances that are converted into a dry, hard, resinous material by the action of oxygen in the air. Examples include the naturally occurring fatty oils such as tung oils, oitica oil, linseed oil, cotton seed oil, perilla oil, unsaturated fish oils, tobacco seed oil, sunflower seed oil, saffron seed oil and S o j ab without nöl. These oils are the tries t er unsaturated ^C -] 2 ~ ^C 22 ^{acids a} and glycerine.

9 0 9820/1288

_ 9 -

The drying oils and nails-drying oils include, for example, partially synthetic, unsaturated substances such as dehydrated! Castor oil, which has a triglyceride structure? fully synthetic substances such as esters of C-jo- ^ o? "unsaturated acids and polyols other than glycerine; partially oxidized oils known as" blown "oils and the partially polymerized oils known as" bodied "oils _o ■

The compound can be a drying or semi-drying oleic acid, which is derived from the oil by saponification, it can be an adduct of the oil or oleic acid or an ester of oleic acid with an acyclic, olefinically unsaturated dicarboxylic acid. Suitably the acyclic, olefinically unsaturated dicarboxylic acid is a 06, beta-ethylenically unsaturated dicarboxylic acid or an anhydride thereof, ζ.B * maleic acid, fumaric acid ,, itaconic acid, and ₉ Agonitsäure alky! Substituted maleic acid with less than 10 carbon atoms in .Each unbroken chain. The conditions for the formation of the product and the reactions involved are known and are commonly referred to as the maleinization of drying oils. They have been described, for example, in British patent specification 1,018,032 ^

Other examples of these compounds are the partially polymerized drying oleic acid, for example dimeric and trimeric acids, such as are found, for example, in US Pat. B. by the company Victor "WoIf Ltd." The processes and conditions for the formation of these acids and their ratios are known and were, for example, by I. F. Byrne B.Sc., FBIC _f Paint Technology, Vol. 26, Mr. 3., pp. 28-38 (1962).

90 98 2 0 / ils-8 "."

- 10 ■ -: V

In addition to improving the service life, numerous improve Compounds also the storage stability of the preparations before the addition of water. The preparations show a tendency on storage to settle the suspended filler and polymerization initiator and to the formation of a hard sediment that only difficult to redisperse. The presence of particular compounds, e.g. the partially polymerized and drying ones oleic acid such as "Dimac S" (Registered Trade Mark) this tendency.

The following examples illustrate those of the invention Preparations made of polyesters and inorganic compounds which can be settled with water

Fillers.

B e 1 s pi e 1 1

There were three unsaturated polyester resins A, B and C with extensive general constituents to an acid number of about 30 mg Kalumhydroxyd per g and condensed in styrene. a 65% by weight solution dissolved the hydroquinone as an inhibitor

contained »

The polyester resin (A) 'was formed by condensing a mixture of phthalic anhydride and maleic anhydride with a mixture of propylene and diethylene glycol. ■ _:

The polyester resin (B) was formed by condensing a Mixture of phthalic and maleic anhydride with diethylene glycol.

The polyester resin (C) was formed by condensing the Phthalic and maleic anhydrides with propylene and polyethylene glycols, _

a 0 9.8 2 0/1288

Those based on these polyester resin / styrene systems "with Water settable preparations were made as follows

Parts by weight

solution of unsaturated polyester resin fin

and styrene (65 wt .- ^ resin in styrene)

"Hydracrete Cement" (entered tr. Goods _n

sign) . 4ü

Connection with an acid or

Anhydride group and a C _in -C / - _{a o}

aliphatic and / or ali-l ^{u DU} ^

cyclic group

Ammonium persulfate 2

Preparations of the above composition were prepared from each of the polyester resins A, B and _{-C and the compounds listed in Table 1 with C 1} Q-CgQ aliphatic and / or alicyelic groups and tested at the specified ratios. 9 parts by weight of water were added to each preparation, then the service life was determined in the following manner.

There were 204 g samples of the above preparations in a dry ^ OO cc cup made from polyethylene and stirred at about 18 ⁰ C. with a palette knife with cutting width of 2.5 cm until homogeneous. Then 18 ecm of water were added and the entire mixture was stirred at 18 ° C. with a palm squeegee until homogeneous. About 50 g of the mixture were poured into a polyvinyl chloride mold of 10 × 5 × 0.625 cm on a glass plate which had previously been treated with a suitable release agent, for example silicone grease. The best of the mixture in the beaker and the cast sample were left to stand at about 18 ° C. The contents of the beaker were gently stirred with the palette squeegee at intervals of about 5 minutes. At first the mixture was thin and

909820/1288

could be stirred very easily, gradually thickening but until it was just flowable and applicable. Then the mixture got too thick to apply and flow and formed gradually a soft, rubbery gel. The time from the addition of water to the point in time when the mixture is just stirred and could be applied with the Palatinate squeegee assumed as lifetime. The cured castings were examined by hand after removal from the mold and the glass plate. Those made from preparations containing Resins B and C Castings were particularly hard and tough after 24 hours.

9 0 9 8 2 0/1288

Tabel

Compound with C ₁ Q-Cg ₀ aliphatic and / or alicyclic groups with unsaturated bonds that can be oxidized in air

Life span of the preparation in min at 18 ⁰ C.

Resin A Resin B Resin C 30th 21 32 30th 21 32 52 62 58 n.u. * n.u. 62 50 59 70 60 63 78 60 54 80 60 75 80 Λ. 66 57 80 55 50 45 72 70 76 70 104 66

Control 1, no connection

Control 2, stearic acid, which contains no oxidizable unsaturated bonds

oleic acid

So bean fat 'urs

Peanut fatty acids tcJ linseed fatty acids ^ tall oil fatty acids ^ non-oil fatty acids to

dehydrated castor oil fatty acids ^ "Blown" flaxseed oil cures (1) N> "bodied" Leinsa & enolfettsUuren (2) oon-dodeceny! succinic anhydride "Dimeric Acid"

(registered trade name of Victor Wolf Ltd.) "Dimeric Acid Anhydrides"

(registered trade name of Victor Wolf Ltd.) * 24 % maleinized linseed oil +15 ^ fumarized saffron seed oil +15 f fumarized methyl ester of saffron seed fatty acids +24 ic maleinized linseed oil fatty acids

n.u.

115

n.u.

108

69

80 54 38 CJ) 85 75 72 CO 75 76 55 -J n.u. 46 45 cn

- H Explanation of symbols for table 1:

n.u. = not examined

(1) "Blown" flaxseed oil fatty acids were those obtained by saponification

of blown linseed oil of an oil viscosity of 30 poise at 25 ⁰ C. fatty acids obtained.

(2) "bodied" Lein3amenöIfettsäuren were the "bodied" by saponification of linseed oil of a Ölviakosität of 150 centistokes at 25 ⁰ C. fatty acids obtained.

* 24 °! ° maleinized flaxseed oil or oleic acid refers to an adduct of 24 parts by weight of maleic anhydride and 76 parts by weight

Share flaxseed oil or its equivalent fatty acid.

+15 $ fumarized oil or oleic ester refers to a Adduct of ο parts by weight of fumaric acid and 85 parts by weight of oil or

Oleic acid ester.

B eia ρ j e 1 2

According to Beisi ^ -? -.rd ° elr. water-settable preparation made from poly-sr and inorganic filler using the unsaturated polyester resin A and 24 fo maleinized linseed oil as a compound with an acid or anhydride group and an aliphatic and / or alicyclic group.

For comparison, two similar preparations were made, in which, however, the maleinized flaxseed oil was replaced by an equivalent Amount of linseed oil or maleic anhydride has been replaced. Each 9 parts by weight of water were added to the preparation, and the tests were then carried out as in Example 1.

909820/1288

The data from these tests are listed in Table 2 and show that neither the linseed oil nor the maleic anhydride tested comparatively results in an extension of the service life.

Table 2

Parts by weight per 100 parts of polyester and
unpfgea. Monomer Flax seed
oil Maleic acid
anhydride Service life in min
at 18 ° C. 24 io maleinis.
Flaxseed oil - - Contr. - - - 30th 3.33 2.5 - 80 - - 0.83 23 - 2.5 0.83 23 - L 3 20th Example]

An unsaturated polyester resin was made from maleic and phthalic anhydride and propylene and polyethylene glycol and condensed to an acid number of about 30 mg KOH / g. The resin was dissolved in styrene to form a 65% strength by weight solution, the hydroquinone as an inhibitor.

According to Example 1, water-settable preparations based on this polyester resin / styrene solution were prepared, using different amounts of "Dimeric Acid" (registered trademark) as a compound with C ₁₀ -CgQ aliphatic and / or alicyclic, unsaturated acid or anhydride groups were used. 9 parts by weight of water were added to each preparation, which was then investigated according to Example 1.

The corresponding data are listed in Table 3.

909820/1288

- 16 - Service life in min
at 18 ⁰ C. Table 3 40 Weight -io added "Dimeric Acid",
based on the weight of polyester
resinous and unsaturated monomers 78 ο (control) 87 0.83 120 1.66 120 2.5 120 3.33 130 5.0 130 8.33 Castings were after 24 10.00 Those made from these preparations Hours resinous and tough. Example 4

An unsaturated polyester resin was prepared from maleic anhydride, phthalic anhydride, propylene glycol and diethylene glycol and condensed to an acid number of 28 mg KOH / g. The resin was dissolved in styrene to form a 65% strength by weight solution which Hydroquinone as an inhibitor contained ...

According to Example 1, water-settable preparations based on this polyester resin / styrene solution were prepared using different amounts of "DJAeric Acid" as a compound with C ₁₀ -Cg ₀ aliphatic and / or alicyclic unsaturated acid or anhydride groups. 9 parts by weight of water were added to each preparation, and the tests were then carried out as in Example 1.

The results are shown in Table 4.

909820/1288

Wt. -Io "Dimeric Acid", ref. To the life in minutes by weight of polyester resin and uncertain sättigtem at 18 ⁰ C. monomers'

0 (control) 57

0.3 100

0.4 120

0.5 130

The castings made from these preparations were after Hours hard and tough.

Example 5_

Using the unsaturated polyester resin C described in Example 1, a water settable one was obtained as follows Preparation made:

Parts by weight ester

uns. polyhara / styrene solution <- _n

(65 Ge /, -% resin in styrene). ^BU

"Kyii'acrete Cement" (eingsWarenseiohan) 20 "Dimeric Acid" (including ₃ trademarks; 1

Ammonium persulfate 2

Gomäß Example 1, the life of this preparation at 18 ⁰ C. after the addition of 4.5 Ge was .; ₅ -'T & ilen water determined? it was five minutes. The service life at 18 ° C. of a comparative preparation without "Dimeric Acid" was 38 minutes. The castings made from these preparations were hard and brittle after 24 hours.

Example 6

According to Example 1, a water-settable preparation was produced, the unsaturated polyester resin C described in Example 1 and "Dimeric Acid" (registered trademark) as a varnish with C-jn ^ GO ali-h ", tables and / or alicyclic un ; ';;^j;: ttlgten ^S: ure- or anhydride groups were used η.

909820/1288

Samples of this preparation were hardened with different amounts of Waaser; and according to Example 1 was at 18 ° G. determines the service life. Samples of a comparison preparation without "Dimeric Acid" were cured in the same way and their service life was determined.

The results are shown in Table 5.

Table 5

Weight of added water per service life at 18 ° C. in min 100 parts by weight hydraulic comparison sample preparation {with filler * (without dimeric dimeric acid) acid)

6.25 11.25 22.5
33.75

The castings made from these preparations were hard and tough after hours.
B e ia ρ i e 1 _ J?

According to example 1, the method described in example 1 was used Polyester resin C produced in the proportions listed there with V / ater settable preparations.

The life span determined according to Example 1 for each preparation is shown in Table 6.

45 180 34 150 32 108 28 76

909820/1288

- 19 table

Compound with C ₁₀ -Cg ₀ aliphatic and / or alicyclic groups with unsaturated groups which can be oxidized at room temperature or a metal salt thereof

Service life in min at 18 ° C.

0 (control) oleic acid

Dimeric Acid (registered trademark from Victor Wolf Ltd.) Potassium oleate Sodium oleate Calcium oleate Potassium salt of "Dimeric Acid" zinc oleate Lead violeate

32 58

108

58 50 60 81 70 i20

The castings made from these preparations were hard and tough after 24 hours.

909820/1288

Claims (9)

Claims 1.- A water-settable preparation made of a polyester and an inorganic, hydraulic filler, consisting of a polymerizable, unsaturated polyester, an ethylenically unsaturated, monomers which can be polymerized with the polyester, an inorganic hydraulic precipitant, which, when mixed with water, has an alkaline reaction shows or initiates and sets to a solid mass, a water-soluble polymerization initiator which, in the substantial absence of water, does not initiate polymerization of the unsaturated monomer and polyester, but becomes active under aqueous alkaline conditions, and 0.1-20 wt .- ^, based on the combined weight of polyester and unsaturated monomer, a compound with at least one acid or anhydride group and a ^ ιη ~ ^ 60 aliphatic and / or alicyclic group with unsaturated bonds, which can be oxidized in air at room temperature, or a Salt of the same in which the positive radical does not accelerate the effectiveness of the polymerization initiator. ₍ 2.- preparation according to claim 1, characterized in that the combined weight of unsaturated polyester and thus inr.schpolymerisbaren monomers, based on the total weight of the preparation, is between 25-85 i ° . 3.- Preparation according to claim 1 and 2, characterized in that the weight of inorganic, hydraulic filler is between 15-75 % . . 909820/1288 - 21 - 4.- preparation according to claim 1 to 3, characterized in that the inorganic hydraulic filler is a hydraulic cement. 5.- preparation according to claim 1 bia 4, characterized in that the compound having at least one acid or anhydride group and a C1-3-C3 aliphitic and / or alicyalic group is partially polymerized, drying oleic acid. 6.- preparation according to claim i to 5, characterized in that it contains an amount of water of 5-40 wt .- $, based on the weight the inorganic hydraulic filler. 7.- preparation according to claim 1 to 6, characterized in that The water-soluble polymerisation initiates a free radical-forming endogenous Redox Polymsrisationainitiators ^ -; tem Lot that one hand oir.e kit oxygenated compound and on the other hand of reducing agents for them. 8.- A process for the production of a water-settable Pr i-.y ir at as from an unsaturated polyester and inorganic, hydraulic! unsaturated polyester, an ethylenically unsaturated, mischpolymerisierbares with the polyester monomer, an inorganic hydraulic filler which is facing yerrühren with water an alkaline reaction or initiates and: setting too "iner solid, a water-soluble polymerisation ii-xti 'ri3initiator, in substantial absence of water does not initiate polymerization of unsaturated monomers and polyesters, but is active under aqueous alkaline conditions 09820/1288 BAt O »* is, and 0.1-20 wt .- ^, based on the combined weight of polyester and unsaturated monomer, a compound with at least one acid or anhydride group and a CQ-Og ₀ aliphatic and / or alicyclic group with unsaturated bonds, those at room temperature . the air can be oxidized, or a salt thereof, in which the positive radical does not accelerate the effectiveness of the polymerization initiator, comprises 9.- Preparations bound with water made from unsaturated polyester and inorganic hydraulic fillers according to the method of claim 8, 10, - Cement and mortar in Igtüi of castings, coatings and stripping boards ("screeä.s") _} contains the preparations according to claim 9. The patent attorney BAD ORiGINAL 909820/1288