IL29256A - Water-setable compositions - Google Patents

Description

C O H E N Z E D E K & S P I S B A C H E G D. PAT E NT ATTO R N EYS 24, LEVONTIN STR., P. O. B . 1169 T E L - A V I V P A T E N T S & D E S I G N S O R D I N A N C E 17421/68 SPECIFICATION WA TEB-SET BLE COMPOSITIONS BRITISH BESIN PRODUCTS LIMITED, a British Company, of Britannic House, Moor La e, London, E.C.2., England , CLARE fhe nature of this invention and in what manner fhe same is to be performed to be particularly described and ascertained in and by the following statement : The present invention relates to, water-setable unsaturated polyester/inorganic hydraulic filler compositions having improved "pot-life", Water-setable unsaturated polyester/inorganic hydraulic filler compositions have been described in British Patent No. 1 ,065 ,053 (Application date 1 th October 1962) .

By "pot-life" is meant throughout this specification and claims the period between the time water is added to set the composition and the time when the composition becomes too thick to be stirred and spread. A relatively long "pot-life" is desirable for most commercial applications so as to enable (a) thorough mixing of the composition with the water used to set the material and with any inert fillers and aggregates which it is desired to add, (b) the mix to be transported from the mixer to the application site and laid properly either by hand trowels, etc., or by mechanical applicators and (c) to allow any surplus mix after application to be cleaned off the mixer and laying tools' or machines.

It is an object of the present invention to provide water-setable polyester/inorganic hydraulic filler compositions having improved "pot-life".

Water-setable polyester/inorganic hydraulic filler compositions according to the present invention comprise a polymerisable unsaturated polyester, an ethylenically unsaturated monomer copolymerisable with said polyester, an inorganic hydraulic filler which after having been stirred with water exhibits or induces an alkaline reaction and sets to a solid mass, a water soluble polymerisation initiator which will not initiate polymerisation of the unsaturated monomer and polyester in the substantial absence of water but which becomes active under aqueous alkaline conditions and 0.1 to 20^ by weight in relation to the combined weight of the polyester and unsaturated monomer of a compound having at least one acid or anhydride group and a aliphatic and/or alicyclic group containing unsaturation capable of being oxidised in air at room temperature or a salt thereof in which the positive radical does not promote the activity of the polymerisation initiator. - The unsaturated polyesters are of the type known from the literature and can be prepared by poly-condensation of a polycarboxylic acid (or anhydride) with a polyhydric alcohol, one of the components having non-aromatic unsaturation capable of undergoing addition polymerisation e.g. ethylenic unsaturation. The dicarboxylic acids, especially the α,β-unsaturated α,β-dicarboxylic acids and dihydric alcohols are mainly used. The unsaturated acids may be partly replaced by a saturated polycarboxylic acid e.g. phthalic or isophthalic acids. It is preferred to use a mixture of saturated and unsaturated dibasic acids together with a glycol. Suitable unsaturated acids are for example, maleic, fumaric, or their - - anhydrides. Suitable dihydric alcohols are for example ethylene glycol, diethylene glycol, propylene glycol and hexylene glycol. Part of the dihydric alcohol may be replaced by polyhydric alcohols such as pentaerythritol or by monohydric alcohols such as cyclohexanol. Suitable polyesters may also be prepared by the alternative route of reacting the polycarboxylic acids or anhydrides with alkylene oxides. Suitable alkylene oxides are ethylene oxide, propylene oxide and butylene oxide.

Suitable ethylenioally unsaturated monomers are known from the literature and include monomeric vinyl and substituted vinyl compounds such as vinyl esters, the esters of acrylic , methacrylic, maleic or fumaric acids, allyl and polyallyl compounds and vinyl aromatic compounds such as styrene. The monomer can be a monomeric vinyl compound in which the polyester is normally dissolved.

The polyesters contain a proportion of unreacted carboxyl groups in the polymer chain and these give it an acid value. Particularly suitable polyesters have acid values of from 10 to 50 milligrams of potassium hydroxide per gram.

Most suitably the combined weight of polyester and copolymeri sable monomer in relation to the total weight of the composition is in the range 5 to %% and preferably in the range 25 to 85?i>. The weight of polyester in relation to the combined weight polyester and monomer is most suitably in the range 20 to 80% and preferably in the range 50 to 70%, The inorganic hydraulic fillers after having been stirred with water exhibit or induce an alkaline reaction which effect is preferably caused by the presence of calcium hydroxide. Examples of such fillers are the hydraulic mortars, in particular the cements such as Portland cement, ferro-Portland cement, blast furnace cement (slag cement) high alumina cement (ciment de la Farge), lime-pozzolana cement, natural cements which are employed in admixture with quicklime and also the hydraulic limes and Roman cement. Portland cement is preferred and such cement is obtained by the heat treatment of a mixture of chalk (or other calcareous earth compound) and clay (or other silicaceous earth compound) but may include any inorganic substance which is hydraulic (i.e. which on mixing with water at ambient temperature reaots to produce a crystalline lattice structure exhibiting a degree of mechanical stability and/or physical strength).. The cements can be any colour and are preferably ground to a powder having a surface area of from 1 ,000 to ,000 square centimetres per gram at the time of incorporation in the composition. Portland cement which has been milled with a fatty acid such as stearic acid produces more stable dispersions when incorporated in the compositions than the cement without the acid. The oleophilic coating of the cement particles also improves the efficiency with which the cement * disperses when added to the polyester and monomer.

The weight of inorganic hydraulic filler in relation to the total weight of the composition can he in the range 5 to 95 percent and is most suitably in the range 15 to 75 percent, About 0 percent by weight of this filler has been found to be the best all round proportion.

The quantity of water used to hydrate the inorganic hydraulic filler and initiate polymerisation of the polyester/ monomer system is preferably in the region of 25 percent based on the weight of this filler present in the composition. Most suitably a minimum water content is about 5 percent and lower strength products are found if the water content exceeds -0 percent by weight. The minimum quantity depends principally on the amount of this filler in the composition. A preferred range is about 15 - 40 percent by weight of water in relation to the filler.

In addition to the inorganic hydraulic filler capable of being set with water an inert non hydratable filler can be present in the composition e.g. silica, sand, gravel, fine and coarse flintstone aggregates, bauxite and other mineral fillers commonly used in the building and allied trades. These additional fillers should be added to the compositions shortly before use.

The water-soluble polymerisation initiators are free radical-forming compounds which are substantially insoluble in the monomer and/or polyester hut can he and pre erably are present as a fine dispersion in the monomer and polyester.

The preferred initiators are active at a pH in the range 7.5 to 11. These compounds are oxygen-rich and particularly suitable examples are the water-soluble salts of peracids such as persulphuric acid, especially ammonium, sodium and potassium persulphate. The free radical-forming compounds can be redox polymerisation initiator systems which comprise the oxygen-rich compounds on the one part and reaotants with these such as reducing agents on the other part. Thus, the salts of peracids may be used as initiators and sulphites used as activators, the two forming a redox initiator system such as that described by C.E.Sohildknecht in "Vinyl and Related Polymers" (Published John Wiley 1952) page 93, Chapter II. The reducing agents are not essential, the salts of peracids being capable of acting as initiators in the presence of Portland cement without added activator. The activator may be any suitable stable reducing agent and sodium metabisulphite is typical, being the preferred but not restricted compound. Other activating materials and/or driers such as cobalt naphthenate may also be present with any other desired conventional additives.

The water soluble polymerisation initiators should be present in an effective amount to initiate polymerisation.

This type of initiator and the amounts in which it can be used are known. Typical quantities are in the range 0.5 to 15 percent by weight in relation to the total weight of unsaturated polyester resin and monomer copolymer!sable therewith.

The compound having at least one acid or anhydride group and a aliphatic and/or alicyclic group containing unsaturation capable of being oxidised in air at room temperature or a salt thereof can be present in the range 0.1 percent to 20 percent by weight in relation to the combined weight of polyester" gnd unsaturated monomer but it is preferable to use 0.2 percent to 5 percent. The compound must be capable of being oxidised at room temperature which is normally a temperature in the range 5°C to 25°C and most suitably in the range 18°C to 20°G. The aliphatic and/or alicyclic group typically contains at least one ethylenically unsaturated group in which the carbon atom to the carbon atom of the unsaturated group is attached to a hydrogen atom i.e. contains the Most suitably the positive radical of the salt is a metal.-Some examples of suitable metal salts are monovalent salts of £fi.kali metals e.g. sodium and potassium; multivalent salts of alkaline earth metals e.g. calcium and salts of other multivalent metals e.g. zinc or lead. Metals which promote the activity of this type of polymerisation initiator and are consequently unsuitable for use as the positive radical are known in the art and probably the most common examples are copper and silver.

Some examples of compounds containing such ethylenic unsaturation are oleic, linoleic, linolenic, ricinoleic, elaeostearic acids, acids derived from fish oils and dicarboxylic acids having alkene radicals such as n-dodecenyl succinic acid. Such compounds do have a measurable iodine value. Suitable compounds have iodine values from 10 to 200 centigrammes per gram.

The compound can be conveniently derived from drying oils and semi-drying oils or from derivatives of these oils. By drying oils and semi-drying oils are meant vegetable or animal oils and certain other liquid substances that are converted by the action of oxygen in the air to a dry, hard, resinous material. Some examples are the naturally occurring fatty oils e.g. tung, oiticia:, linseed, cotton-seed, perilla, unsaturated fish oils, tobacco seed, sunflower seed, safflower seed and soya bean oils. These oils are the triesters of unsaturated 2 - acids and glycerol.

The drying oils and semi-drying oils include for example partially synthetic unsaturated substances such as dehydrated castor oil which has a triglyceride structure; wholly synthetic substances such as esters of - unsaturated acids and polyols other than glycerol; partially oxidised oils known as blown oils and the partially polymerised oils known as bodied oils.

The compound can be a drying or semi-drying oil acid derived from the oil by saponification. It can be an adduct of the oil, or the oil acid or ester of the oil acid with an acyclic olefinically unsaturated dicarboxylic acid. Most suitably the acyclic olefinic unsaturated dicarboxylic acid is an α,β-ethylenically unsaturated dicarboxylic acid or an anhydride thereof e.g. maleic, fumaric, aoonitic, itaconic and alkyl substituted maleic acids having less than 10 carbon atoms in any uninterrupted chain. The conditions for the formation of the adduct and the reactions involved are well known and are commonly referred to as the maleinisation of drying oils. They have been described for example in British Patent 1,018,032.

Other examples of these compounds are the partially polymerised drying oil acids e.g. dimeric and trimeric acids of the type produced by for example Victor ¥olf Ltd. The processes and conditions for the formation of these acids and their properties are well known and have been described for example by L.F. Byrne B.Sc, P.R.I.C., Paint Technology, Vol.26, No.3, p.28-38 (1962).

In addition to improving "pot-life" a number of the compounds also improve the storage stability of the compositions prior to addition of water. The compositions on storage exhibit a tendency for the suspended filler and polymerisation initiator to settle out and form a hard sediment which is difficult to redisperse. The presence of particular compounds e.g. the partially polymerised drying oil acids such as mac S (A Registered Trade Mark) reduces this tendency.

The following examples illustrate water-setable polyester/inorganic filler compositions according to the present invention.

Example 1 Three unsaturated polyester resins A, B and C having the following general constituents were each condensed to an acid value of approximately 30 milligrams of potassium hydroxide per gram and dissolved in styrene to give a 65 percent by weight solution containing hydroquinone as inhibitor.

Polyester resin (A) is formed by condensing a mixture of phthalic and maleic anhydrides with a mixture of propylene and diethylene glycols.

Polyester resin (B) is formed by condensing a mixture of phthalic and maleic anhydrides with diethylene glcyol.

Polyester resin (c) is formed by condensing phthalic and maleic anhydrides with propylene and polyethylene glycols.

Water-setable compositions based on these polyester resin/styrene systems were made up in accordance with the following recipe. unsaturated polyester resin/styrene 60 parts by weight solution {S5% by weight of resin in styrene.

Hydracrete Cement (A Registered fl parts by weight Trade Mark) .

Compound having an acid or anhydride 2 parts by weight group and a - Cg^ aliphatic and/or ali cyclic group.

Ammonium Persulphate 2 parts by weight Compositions having the above mentioned recipe were made up from each of th e polyester resins A , B and C and the compounds having aliphatic and/or alicyclic groups listed in Table 1 were tested in each composition in the proportion given . 9 parts by vreight of water was added to each composition and its "pot-li e" estimated in the following manner. 204 gram samples of the above mentioned composition s were prepared in a 1+00 ml . dry polyethylene beaker and stirred at approximately 1 8°C with a 1 inch wide bladed palette knife until homogeneous . 1 8 mis water were then added and the total mix was stirred at 1 8°C with thepalette knife until homogeneous.

Approximately 50 grams of the mix was poured into a inch x 2 inch x ¾ inch deep polyvinyl chloride mould placed on a glass plate previously treated with a suitable parting agent e . g. silicone grease . The remainder of the mix in th e beaker and the poured cast were allowed to stand at approximately 1 8°C .

The contents of the beaker were stirred gently at approximately 5 minute intervals with the palette knife . The mix at first was thin and could b e stirred very easily but gradually thickened until it was just capable of flowing and spreading . The mix then became too thick to spread and flow easily and eventually formed a soft rubbery gel. The time from the water addition to the point where the mix could just be stirred and spread with the palette knife was taken as the "pot-life". Cured casts were examined by hand after removal from the mould and glass plate.. Casts made from compositions containing resins B and C were particularly hard and tough after 2 hours.

TABLE 1 Compound having - aliphatic Pot Life of Composition and/or alicyclic groups containing in Minutes at 18°C . unsaturation capable of being oxidised in air. Resin A Resin B Resin C Control 1 . No compound 30 21 32 Control 2. Containing Stearic Acid 30 21 32 which does not have oxi disable unsaturation.

Oleic acid 52 62 58 Soya Bean Patty Acids NE NE 62 Ground Nut " " ': 50 59 70 Linseed Oil " " 60 63 78 Tall Oil " " 60 54 80 Tung Oil " " 60 75 80 Dehydrated Castor Oil Fatty Acids 66 57 80 Blown Linseed Oil Patty Acids ( ) 55 50 45 Bodied Linseed Oil Fatty Acids (2) 72 70 76 n Dodecenyl Succinic Anhydride 70 104 66 Dimeric Acid (Dilinoleic Acid) 100 115 108 (A Regd. Trade Mark of Victor Wolf I ,td) Dimeric Acid Anhydride j NE NE 69 (A Regd. Trade Mark of Victor Wolf Ltd) *22$ Maleinised Linseed Oil 80 54 38 +15 Fumarised Saf flower Seed Oil 85 75 72 + 5% Fumarised Methyl Ester of 75 76 55 Saff lower Fatty Acids +2 Maleinised Linseed Oil NE 46 45 Fatty Acids NE = Not examined (1 ) Blown Linseed Oil Patty Acids were the fatty acids obtained by saponification of Blown Lins eed Oil of oil viscosity 30 poi se at 25°C (2) Bodied Linseed Oil Fatty Acids were the fatty acids obtained by saponification of Bodied Linseed Oil of Oil viscosity 150 c en ti stokes at 25 tC . *22$ Maleinised linseed oil or oil acid refers to an adduct of 2 parts by weight maleic anhydride and 76 parts by weight linseed oil or its corresponding fatty acid. +1 fumarised oil or oil acid ester refers to an adduct of 1 parts by weight of fumaric acid and 85 parts by weight of oil or oil acid ester.

Example 2 A water-setable/inorganic filler composition was made up in a manner describ ed in Exampl e 1 using unsaturated polyester resin A and 21 maleinised linseed oil as the compound having an acid or anhydride group and an aliphatic and/or alicyclic group.

By way of comparison , two similar compositions were made up differing in that the maleini sed linseed oil was replac ed by an equivalent quantity of , in one case linseed oil and in the other case , maleic anhydride . 9 parts by weight of water was added to each composition which was examined using the same proc edure as described for Example 1..

The data obtained from these experiments i s given in Table 2 which illustrates that neither linseed oil nor maleic anhydride given by way of comparison gives an extension of "pot-life" .

TABLE 2 An unsaturated polyester resin was prepared from maleic and phthalic anhydrides and propylene and polyethylene glycols condensed to an acid value of approximately 30 milligrams of KOH/ ram. The resin waa dissolved in styrene to give a by weight solution containing hydroquinone as inhibitor.

Water-setable compositions based on this polyester resin/styrene solution were made up in the manner described in Example 1 using various amounts of Dim eric Acid (A Registered Trade Mark) as the compound having C - n - C,-n aliphatic and/or alicyclic unsaturated acid or anhydride groups. 9 parts by weight of water were added to each composition which was examined using the same procedure as described in Example 1 .

The data obtained from these experiments is given in Table 3· Casts made from the compositions were hard and tough after 2h hours.

Example An unsaturated polyester resin was prepared from maleic anhydride, phthalic anhydride, propylene glycol and di ethylene glycol and condensed to an acid value of 28 mg. KOH/gram. The resin was dissolved in styrene to give a 65% by weight solution containing hydroquinone as inhibitor.

Water setable compositions based on this polyester resin/ styrene solution were made up in the manner described in Example 1 using various amounts of Dimeric Acid (A Registered Trade Mark) as the compound having aliphatic and/or alicyclic unsaturated acid or anhydride groups. 9 parts by weight of water were added to each composition which was examined using the same procedure described in Example 1.

The data from these experiments are given in Table · Casts made from these compositions were hard and tough hours.

A water setable composition was made up in the manner described below using unsaturated polyester resin C as described in Example 1 · Unsaturated polyester resin/styrene 60 parts by weight solution (65 > by weight of resin in styre e) Hydracrete Cement (A Regd. Trade Mark) 20 parts by weight Dim eric Acid (A Regd. Trade Mark) 1 part by weight Ammonium Persulphate 2 parts by weight The "pot-life" at 18°C of this composition after the addition of 4·5 parts by weight of water was determined in the manner described in Example 1 and was found to be 170 minutes. The "pot-life" at 18°C of a control composition omitting the Dimeric Acid (A Regd. Trade Mark) was 38 minutes. Casts made from these compositions were hard and brittle , after 24 hours. Example 6.

A water setable composition was made up in the manner described in Example 1 using unsaturated polyester resin C described in Example 1 and Dimeric Acid (A Regd. Trade Mark) as the C.JQ- aliphatic and/or alicyclic unsaturated acid or anhydride.

Samples of this composition were cured using different amounts of water and the 'pot-lives" at 18°C were determined in the manner described in Example 1 . Samples of the control composition omitting the Dimeric Acid were cured in exactly the same manner and their "pot-lives" determined.

The results of this experiment are given in Table 5· W eight of Water added per Pot Life at 18°C in minutes 100 parts by weight of hydraulic filler. Control Composition Composition (Without Dimer c (With DimericJ Acid) Acid) 6.25 5 180 11 .25 1 0 22.5 32 108 33.75 28 76 Casts from these compositions were hard and tough after 2 hours.

Example 7.

Water setable compositions were made up using polyester resin C as described in Example 1 in the manner and proportions described in Example .

The "pot-life" of each composition was deterinined in the manner described in Example 1 and the results of this experiment are given in Table 6.

TABLE 6 Casts made from these compositions nere hard and tough after 2 hours.

Claims (11)

What we claim is :

1. A water setable polyester/inorganic hydraulic filler composition which comprises a polymerisable unsaturated polyester, an ethylenically unsaturated monomer copolymerisable with said polyester, an inorganic hydraulio filler which after having been stirred with water exhibits or induces an alkaline reaction and sets to a solid mass, a water soluble polymerisation initiator which will not initiate polymerisation of the unsaturated monomer and polyester in the substantial absence of water but which becomes active under aqueous alkaline conditions and 0.1 to 20% by weight in relation to the combined weight of the polyester and unsaturated monomer of a compound having at least one acid or anhydride group and a - aliphatic and or alicyolic group containing unsaturation capable of being oxidised in air at room temperature or a salt thereof in which the positive radical does not promote the activity of the polymerisation initiator.

2. A composition as claimed in Claim 1 wherein the combined weight of unsaturated polyester and monomer copolymerisable therewith in relation to the total weight of the composition is in the range 25 to 85 percent.

3. A composition as claimed in either claim 1 or claim 2 wherein the weight of inorganic hydraulic filler is in the range 15 to 15%. if.

4. A composition as claimed in any one of the preceding claims wherein the inorganic hydraulic filler is a hydraulic cement.

5. A composition as claimed in any one of the preceding claims wherein the compound having at least one acid or anhydride group and a - aliphatic and/or al cyclio group is a partially polymerised drying oil acid,

6. A composition as claimed in any one of the preceding claims in combination with an amount of water ranging from 5 to l£>% by weight in relation to the weight of inorganic hydraulic filler.

7. A composition as claimed in any one of the preceding claims wherein the water soluble polymerisation initiator is a free radical forming redox polymerisation initiator system which comprises an oxygen rich compound on the one part and a reducing agent therefor on the other part,

8. A composition as claimed in claim 1 and as described in any one of the Examples.

9. » A method for making a setablo unsaturated polyester/ inorganic hydraulic filler composition which comprises adding water to a stable, substantially water-free mixture comprising a polymerisable unsaturated polyester, an ethylenically unsatured monomer copolymer! sable with said polyester, an inorganic hydraulic filler which after having been stirred with water exhibits or induces an alkaline reaction and sets to a solid mass, a water soluble polymerisation initiator which will not initiate polymerisation of the unsaturated monomer and polyester in the substantial absence of water but which becomes active under aqueous alkaline conditions and 0.1 to 20% by weight in relation to the combined weight of the polyester and unsaturated monomer of a compound having at least one acid or anhydride group and a - Cg^ aliphatic and/or alicyclic group containing unsaturation capable of being oxidised in air at room temperature or a salt thereof in which the positive radical does not promote the activity of the polymerisation initiator.

10. A method for making a setable unsaturated polyester/ inorganic hydraulic filler composition as claimed in claim 9 and as hereinbefore described with reference to any one of the Examples.

11. . Water set unsaturated polyester/inorganio hydraulic filler compositions when made by the method as claimed in either claim or claim 10. . Concrete and mortars as castings, coatings and soreeds containing the compositions as claimed in claim 11 . DATED THIS 1st da GOHSl ZSDS & SP3SBAGH P.O.BOX 1169» TlXr-AVIV A tt orneys £ o∑ Applicants BDE/MS.