GB2087416A - Low shrinking resin mortar or resin concrete composition - Google Patents

Low shrinking resin mortar or resin concrete composition Download PDF

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GB2087416A
GB2087416A GB8133202A GB8133202A GB2087416A GB 2087416 A GB2087416 A GB 2087416A GB 8133202 A GB8133202 A GB 8133202A GB 8133202 A GB8133202 A GB 8133202A GB 2087416 A GB2087416 A GB 2087416A
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resin
block copolymer
mixture
weight
parts
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NOF Corp
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Nippon Oil and Fats Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A resin mortar composition or resin concrete composition comprising (a) a low shrinking resin, which consists of a block copolymer mixture, (b) an unsaturated polymer and (c) a monomer copolymerizable therewith as a binder, and (d) a filler and/or aggregate, is low in shrinkage and has excellent dimensional stability. The block copolymer mixture is obtained by firstly polymerizing vinyl acetate, or a styrene series monomer, and/or an acrylic acid ester and/or a methacrylic acid ester, in the presence of a polymerization initiator of a polymeric peroxide having the following general formula <IMAGE> to form a mixture of a copolymer having peroxy bonds in the molecule, and then copolymerizing the copolymer mixture with another monomer, to form a mixture of block copolymer and the component polymers.

Description

SPECIFICATION Low shrinking resin mortar or resin concrete composition The present invention relates to a low shrinking resin mortar composition or resin concrete composition containing a binder resin consisting mainly of an unsaturated polyester and a block copolymer mixture and having excellent dispersion stability.
Resin mortar or resin concrete formed of a hardening resin used as a binder in place of Portland cement and at least one of inorganic filler (such as calcium carbonate or the like) and aggregate (which consists mainly of sand, gravel and the like) is generally superior to cement mortar or concrete in the chemical resistance, water resistance, acid resistance, dust-resistant property, electrically insulating property and curability, and is further light in weight. Therefore, the resin mortar or resin concrete has recently been developed and used for civil engineering, electric apparatus, chemical engineering and the like.
However, conventional resin mortar or resin concrete produced by using unsaturated polyester resin as a binder shrinks during the curing, and often cracks. Therefore, the conventional resin mortar or resin concrete has serious drawbacks in the use as a structural material.
In order to suppress the shrinkage of resin mortar or resin concrete during the curing and to adjust its dimension to a desired dimension, there has been proposed a method, wherein unsaturated polyester is mixed with a thermoplastic resin, such as polystyrene or the like, as a low shrinking agent. However, polystyrene is poor in the compatibility with unsaturated polyester, and therefore polystyrene is easily separated from unsaturated polyester during the mixing. While, even when a thermoplastic resin, for example, vinyl acetate, having good compatibility with unsaturated polyester is used, the thermoplastic resin is separated from unsaturated polyester during the curing. Therefore, resin mortar or resin concrete having a stable dimension has not yet been obtained.Japanese Patent Laid Open Application No. 47,859/77 discloses a method, wherein a dispersion stabilizer consisting of a comb-shaped copolymer, which has a main chain formed of a styrene series polymer and a side chain formed of a saturated polyester segment, is added to a binder resin in order to prevent separation of the low shrinking agent from the unsaturated polyester. However, the addition of such component makes the operation troublesome, and is not yet satisfactory.
The inventor has found that, when a monomer is polymerized in the presence of a polymeric peroxide as a polymerization initiator to form a mixture of a copolymer having peroxy bonds in the molecule, and then the copolymer mixture is block copolymerized with another monomer, the resulting block copolymer mixture consists of a block copolymer and a homopolymer of the above described monomer and contains a large amount of the block copolymer in a high block efficiency of 7080%.
Therefore, nonaqueous solvent-dispersible resin composition containing this block copolymer mixture has very excellent dispersion stability. The inventor takes a notice of this point and has made various investigations with respect to resin mortar or resin concrete, which uses a binder consisting of a mixture of an unsaturated polyester and a block copolymer mixture obtained by using a polymeric peroxide, in order to overcome the drawback of conventional resin mortar or resin concrete.As the results, the inventor has found that a binder consisting of a low shrinking resin consisting of a block copolymer mixture which is obtained by copolymerizing vinyl acetate or a monomer mixture consisting of vinyl acetate and a monomer copolymerizable therewith with other monomer, an unsaturated polyester and a monomer copolymerizable with the unsaturated polyester has a dispersion stability higher than that of any other conventional resin binders, and that a resin mortar composition or resin concrete composition containing the above described binder and at least one of filler and aggregate is small in the volume shrinkage and has excellent dimensional stability, and has accomplished the present invention.
The feature of the present invention is the provision of a low shrinking resin mortar composition or resin concrete composition comprising a low shrinking resin consisting (a) a block copolymer mixture, (b) unsaturated polyester and (c) a monomer copolymerizable with said unsaturated polyester, said low shrinking resin being used as a binder, and (d) a filler and/or an aggregate; said block copolymer mixture being obtained by firstly polymerizing one of the following monomers (i) and (ii), (i) 10-90 parts by weight of a monomer consisting of 70-i 00% by weight of vinyl acetate and 300% by weight of a monomer copolymerizable with vinyl acetate, and (ii) 90-10 parts by weight of a monomer consisting of 0-100% by weight of a styrene series monomer and 1000% by weight of an acrylic acid ester andlor methacrylic acid ester, in the presence of a polymerization initiator of a polymeric peroxide having the following general formula
wherein R, represents an alkylene group or substituted alkylene group having 1-1 8 carbon atoms, a cycloalkylene group or substituted cycloalkylene group having 3-1 5 carbon atoms, or a phenylene group or substituted phenylene group; R2 represents an alkylene group or substituted alkylene group having 2-10 carbon atoms,
(wherein R3 represents a hydrogen atom or a methyl group, R4 represents an alkylene group or substituted alkylene group having 2-10 carbon atoms, and m represents an integer of 1-13),
and n represents an integer of 2-20; to form a mixture of a copolymer having peroxy bonds in the molecule, and then copolymerizing the copolymer mixture with another monomer.
The block copolymer mixture to be used in the present invention can be easily produced from the above described monomers (i) and (ii) through a commonly known bulk polymerization process, suspension polymerization process, emulsion polymerization process, solution polymerization process or the like by using, as a polymerization initiator, the polymeric peroxide represented by the general formula (I). In this case, the copolymer having peroxy bonds the molecule, which is produced by the first polymerization reaction, can be taken out as an intermediate from the reaction system and used as a raw material for the production of a block copolymer in the next step, or can be block copolymerized with another monomer without being taken out from the reaction system. When the use amount of the polymeric peroxide is 0.1-10 parts by weight based on 100 parts by weight of the above described monomer mixture shown by the monomer (i) or (ii), the polymerization temperature is 4090 C and the polymerization time is 2-1 5 hours, a good result can be obtained.
The polymeric peroxide to be used in the production of the block copolymer mixture in the present invention can be easily produced by reacting a dibasic acid chloride having ester linkages in the molecule with sodium peroxide in a commonly used method for producing diacyl peroxide.
As the polymeric peroxide represented by the general formula (I) according to the present invention, there can be used, for example,
and the like. In the above described formulae, n represents an integer of 2-20.
In the present invention, it is necessary that the binder resin contains 120% by weight of the block copolymer mixture. When the amount of the block copolymer mixture is less than 1% S/o by weight, a resin mortar or resin concrete composition having a satisfactorily low shrinkage cannot be obtained.
While, when the amount exceeds 20% by weight, the workability and mechanical property of the resulting resin mortar or resin concrete composition are poor.
The unsaturated polyesters to be used in the present invention are ones obtained through a polycondensation of cz unsaturated dibasic acid, saturated dibasic acid and glycol by a commonly known method. The a,-unsaturated dibasic acids include maleic acid anhydride, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, alkyl esters of these acids and the like. The saturated dibasic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, halogenated phthalic acid anhydride, adipic acid, succinic acid, sebacic acid, alkyl esters of these acids and the like.The glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, hydrogenated bisphenol A, 2,2'-di(4-hydroxypropoxyphenyl)propane, 2,2'-di(4-hydroxyethoxyphenyl)propane, ethylene oxide, propylene oxide and the like.
The monomers copolymerizable with the above described unsaturated polyester and used in the present invention include styrene series monomers, such as styrene, vinyltoluene, (Z-methylstyrene, t butylstyrene, chlorostyrene and the like; diallyl phthalate, vinyl acetate, acrylic acid esters, methacrylic acid esters and the like. Among them, styrene series monomers are preferable.
As the catalyst for curing the low shrinking resin of the present invention, use is made of commonly known catalysts used in the curing of unsaturated polyester. The catalysts are, for example, diacyl peroxide, ketone peroxide, alkyl peroxide, hydroperoxide, peroxide ester and the like. These curing catalysts can be occasionally used together with promoters, for example, organic metal salts, such as cobalt naphthenate, cobalt octylate and the like, aliphatic amines, aromatic amines, mercaptanes and the like.
The fillers to be used in the present invention are ones commonly used in unsaturated polyester resin composition, and are calcium carbonate, perlite, talc and the like.
As the aggregates to be used in the present invention, use is made of river sand, sea sand, crushed stone, silica powder, marble sand, silicon carbide, zircon sand and the like. The filler and/or aggregate are preferably used in an amount of 1-20 times (by weight) of the amount of the resin.
The block copolymer mixture of the present invention has a high block efficiency, and contains a small amount of a polymer other than a block copolymer. Therefore, the low shrinking resin consisting mainly of the block copolymer mixture and the unsaturated polyester according to the present invention is very high in the dispersion stability, and the resin mortar composition or resin concrete composition containing the low shrinking resin does not cause separation of the low shrinking agent during shaping and is excellent in the dimensional stability.
The resin mortar composition or resin concrete composition of the present invention may contain reinforcing agents, such as glass fibers, polyester fibers and the like; thickeners, such as magnesium oxide, magnesium hydroxide, calcium oxide and the like; coloring agent; releasing agent and the like, which are commonly used for unsaturated polyester resin compositions.
The following examples are given for the purpose of illustration of this invention and are not intended as limitations thereof. In the examples, "parts" and "%" mean parts by weight and % by weight respectively unless otherwise indicated.
Reference Example 1 Production of
In a glass reaction vessel equipped with a thermometer and a stirrer were charged 1 83 parts of adipic acid chloride and 75 parts of triethylene glycol, and the resulting mixture was reacted at a temperature of 2O-3O0C for 60 minutes under stirring while maintaining the pressure to 40-50 mmHg to obtain 220 parts of colorless viscous liquid triethyiene glycol-bis(adipoyl chloride).
An aqueous sodium peroxide solution previously prepared from 30 parts of 50% aqueous hydrogen peroxide solution and 832 parts of 5% aqueous sodium hydroxide solution was charged into another glass reaction vessel equipped with a thermometer, a stirrer and a dropping funnel. Then, 1 76 parts of the above obtained triethylene glycol-bis(adipoyl chloride) was added dropwise to the aqueous sodium peroxide solution from the dropping funnel while maintaining the reaction temperature to 0--5 0 C under stirring. After completion of the addition, the stirring was further continued for 30 minutes while maintaining the temperature of the reaction system to 0-50C to complete the reaction.
The resulting solid precipitate was filtered, washed with water 2 times and dried under vacuum to obtain 140 parts of a white solid. The white solid was purified through a recrystallization, wherein the white solid was dissolved in 360 parts of chloroform and the chloroform solution was poured into 1,600 parts of methanol. The purified product was filtered to obtain 108 parts of a white solid. The resulting white solid had the following characteristic values and was ascertained to be the polymeric peroxide
The molecular weight was measured by VPO (apparatus for measuring molecular weight by the process of gas pressure equilibrium, Model 11 5, made by Hitachi Seisakusho Ltd.).
Purity by iodometry 99.7% Decomposition temperature 900C Molecular weight 2,140 (n =5.3) infrared absorption spectrum 1,725 cam~1 (C = 0 bond assigned to ester group) 1,780 cm-' and 1,805 cm-' (C = 0 bond assigned to diacyl group) 875 cm-l (O = 0 bond) Nuclear magnetic resonance spectrum
T6. 28 (aH. -C112CH2 OCH2-)
Reference Example 2 Production of
Into a glass reaction vessel equipped with a thermometer and a stirrer were charged 406 parts of isophthalic acid chloride, 228 parts of 2,2-di(4-hydroxyphenyl)propane and 1,500 parts of toluene, and the resulting mixture was reacted at a temperature of 7O-750C for 2 hours while blowing nitrogen to obtain 2,020 parts of a toluene solution of coiorless liquid 2,2-di(4-hydroxyphenyl)propanebis(isophthaloyl chloride). This toluene solution contained 27.5% of the acid chloride.
Then, the toluene solution was treated according to the production method and purification method described in Reference Example 1 to obtain 325 parts of a white solid. The resulting white solid had the following characteristic values and was ascertained to be the polymeric peroxide
Purity by iodometry 97.5% Decomposition temperature 1 2O0C Molecular weight 1,829 (n = 3.5) Infrared absorption spectrum 1,720 cm-' (C = 0 bond assigned to ester group) 1,770 cam~' and 1,790 cm- (C = 0 bond assigned to diacyl group) 865 cm-l (O = 0 bond) Reference Example 3 Production-1 of a vinyl acetate-styrene block copolymer mixture Into a glass reaction vessel equipped with a thermometer, a stirrer and a condenser were charged 300 parts of a 1% aqueous solution of polyvinyl alcohol and a solution previously prepared by dissolving 0.5 part of the polymeric peroxide obtained in Reference Example 1 in 10 parts of vinyl acetate. After air in the vessel was replaced by nitrogen gas, the mixture in the vessel was heated to 600C to start a polymerization reaction, and the polymerization reaction was continued for 3 hours while maintaining the temperature to 6O0C. Then, 90 parts of styrene was added to the reaction system, and the polymerization reaction was further continued at 750C for 7 hours.After the reaction mass was cooled to room temperature to finish the polymerization reaction, the polymerization product was filtered, washed thoroughly with water and then dried under vacuum to obtain 97 parts of a white granular block copolymer mixture.
Reference Example 4 Production-2 of a vinyl acetate-styrene block copolymer mixture The procedure of Reference Example 3 was repeated, except that 10 parts of styrene and a solution previously prepared by dissolving 2.5 parts of the polymeric peroxide obtained in Reference Example 1 in 50 parts of vinyl acetate were used, to obtain 97 parts of a block copolymer mixture.
Reference Example 5 Production-3 of a vinyl acetate-styrene block copolymer mixture The procedure of Reference Example 3 was repeated, except that 10 parts of styrene and a solution previously prepared by dissolving 4.5 parts of the polymeric peroxide obtained in Reference Example 1 in 90 parts of vinyl acetate were used, to obtain 96 parts of a block copolymer mixture.
Reference Example 6 Production-4 of a vinyl acetate-styrene block copolymer mixture The procedure of Reference Example 3 was repeated, except that a solution previously prepared by dissolving 0.75 part of the polymeric peroxide obtained in Reference Example 2 in 10 parts of vinyl acetate was used, to obtain 95 parts of a block copolymer mixture.
Then, the block efficiency of the vinyl acetate-styrene block copolymer mixtures obtained in the above described Reference Examples 3, 4, 5 and 6 was determined in the following manner. That is, 2.0 g of each of the vinyl acetate-styrene block copolymer mixtures was weighed, and extracted firstly by methanol for 24 hours and then by cyclohexane for 24 hours by means of a Soxhlet extractor. The decreased weight by the methanol extraction shows the content of polyvinyl acetate (PVAC), the decreased weight by the cyclohexane extraction shows the content of polystyrene (PST), and the amount of the extraction residue shows the content of vinyl acetate-styrene block copolymer.Further, the nuclear magnetic resonance spectrum of the block copolymer of the extraction residue was measured, and the ratio (ST/VAC) of units constituting the block copolymer was calculated from the intensity ratio of the chemical shift (T 3.0, 3.5) of benzene ring proton of styrene (ST) unit to the chemical shift (T 5.1) of -methine proton of vinyl acetate (VAC) unit, and the amount of styrene introduced into the block copolymer by the polymerization reaction (amount of styrene units in the block copolymer) was divided by the total amount of polymerized styrene (sum of the amount of polystyrene and the amount of styrene units in the block copolymer), whereby the block efficiency was calculated.
The obtained results are shown in the following Table 1.
TABLE 1
Composition of VAC-ST block copolymer mixture Ratio of units Feed ratio VAC-ST constituting of monomers block VAC-ST block Block (ST/VAC) PST PVAC copolymer copolymer efficiency (%) Reference 90/10 8.2 0.9 90.9 91/9 91 example 3 Reference example 4 50/50 8.3 4.5 87.2 49/51 84 Reference example 5 10/90 2.4 9.7 87.9 8/92 75 Reference example 90/10 8.3 1.0 90.7 91/9 91 Reference Example 7 Production of a vinyl acetate-methyl methacrylate block copolymer mixture Into a glass reaction vessel equipped with a thermometer, a stirrer and a condenser were charged 300 parts of a 0.2% aqueous solution of polyvinyl alcohol and a solution previously prepared by dissolving 0.5 part of the polymeric peroxide obtained in Reference Example 1 in 10 parts of vinyl acetate. After air in the vessel was replaced by nitrogen gas, the mixture in the vessel was heated to 6O0C to start a polymerization reaction, and the polymerization reaction was continued for 3 hours while maintaining the temperature to 600 C. Then, 90 parts of methyl methacrylate was added to the reaction system, and the polymerization was further continued at 700C for 5 hours. After the reaction mass was cooled to room temperature to complete the polymerization reaction, the polymerization product was filtered, washed thoroughly with water and then dried under vacuum to obtain 96 parts of a white granular block copolymer mixture.
Reference Example 8 Production of an unsaturated polyester resin A mixture of 464 parts of fumaric acid and 888 parts of phthalic acid anhydride was esterified with a mixture of 403 parts of propylene glycol and 625 parts of hexylene glycol by a conventional method to produce an unsaturated polyester (acid value: 31.5). In 40 parts of styrene was dissolved 60 parts of the above obtained unsaturated polyester together with 0.01 part of hydroquinone to obtain an unsaturated polyester resin.
EXAMPLE 1 In a labomixer (high shear mixer), 80 parts of the unsaturated polyester resin obtained in Reference Example 8 was mixed for 20 minutes with 20 parts of a styrene dispersion of the block copolymer mixture obtained in Reference Example 3, which dispersion had previously been prepared by dispersing the block copolymer mixture in styrene and had a concentration of the block copolymer mixture of 30%. Then, the mixture was mixed with 1.0 part of methyl ethyl ketone peroxide and 0.3 part of cobalt naphthenate, and further mixed with 100 parts of a mixture of aggregate and filler (the mixture consisted of 2 parts of borax No. 3, 1 part of borax No. 4, 1 part of borax No. 7 and 1 part of calcium carbide) to obtain a resin mortar composition.The resulting composition was cured for 2 hours at room temperature, and aged for 7 days. After the aging, the surface of the cured resin mortar composition was observed, and the shrinkage thereof was measured. As the results, it was found that the surface state is good without formation of crack and deformation and the linear shrinkage was 0.02%.
Comparative Example 1 A resin mortar composition was produced and cured in the same manner as described in Example 1, except that polystyrene (made by Asahi Dow Industrial Co., Styron 666) was used in place of the block copolymer mixture used in Example 1. As the results, the surface of the cured product had stickiness probably due to the separation of polystyrene, and it was impossible to measure the shrinkage.
EXAMPLES 2-5 In a labomixer, 80 parts of the unsaturated polyester resin obtained in Reference Example 8 was mixed for 20 minutes with 20 parts of a styrene dispersion of each of the block copolymer mixtures obtained in Reference Examples 3, 4, 6 and 7, which dispersion had previously been prepared by dispersing the block copolymer mixture in styrene and had a concentration of the block copolymer mixture of 30%. Then, the resulting mixture was mixed with 1.0 part of methy ethyl ketone peroxide and 0.3 part of cobalt naphthenate, and further mixed with 100 parts of calcium carbonate and 300 parts of river sand (maximum diameter: 5 mm) to obtain a resin concrete composition.Then, the composition was injected into a metal mold having a dimension of a length of 1 ,000 mm, a width of 100 mm and a height of 50 mm, cured for 2 hours at room temperature, and aged for 7 days to obtain a resin concrete having a good surface. The obtained results are shown in Table 2.
Comparative Example 2 A resin concrete was produced in the same manner as described in Examples 2-5, except that the styrene dispersion of block copolymer mixture described in Examples 2-5 was not used. The surface state was poor due to the formation of flaw and crack. The obtained results are shown in Table 2.
Comparative Example 3 A resin concrete was produced in the same manner as described in Examples 2-5, except that polystyrene was used in place of the block copolymer mixture used in Examples 2-5. The resulting resin concrete had stickiness probably due to the separation of polystyrene, and it was impossible to measure the shrinkage. The obtained results are shown in Table 2.
Comparative Example 4 A resin concrete was produced in the same manner as described in Examples 2-5, except that a vinyl acetate series low shrinking agent, Epolac AT--300 (made by Nippon Shokubai Kagaku Kogyo Co.
Ltd., solid content: 30%), was used in place of the styrene dispersion of block copolymer mixture used in Examples 2-5. The surface of the resulting resin concrete had stickiness probably due to the separation of polyvinyl acetate, and it was impossible to measure the shrinkage. The obtained results are shown in Table 2.
TABLE 2 Results of Evaluation of resin concrete
Surface state of Shrinkage *2 Low shrinking agent resin concrete *1 (%) block copolymer of Example 2 Reference example 3 0 0.01 block copolymer of Example 3 Reference example 4 O 0.01 block copolymer of Example 4 Reference example 6 0 0.01 block copolymer of Example 5 Reference example 7 0 0.02 Comparative example 2 not added x 0.20 Comparative example 3 polystyrene x Comparative example 4 polyvinyl acetate x Note: *1: o indicates good surface state x indicates poor surface state due to formation of crack or separation of'low shrinking agent *2: Measurement of shrinkage in Comparative examples 3 and 4 was impossible due to poor surface state.
It can be seen from Table 2 that the resin concrete produced by using the block copolymer mixture of the present invention has good surface state and is excellent in the low shrink property.
EXAMPLES 6-8 Resin concrete compositions were produced in the same manner as described in Examples 2-5, except that 1 00 parts of a mixture of the unsaturated polyester resin (UPR) obtained in Reference Example 8 and a 30% styrene dispersion (A) of the vinyl acetate-styrene block copolymer mixture obtained in Reference Example 3 in a mixing ratio of UPR/A shown in the following Table 3 was used in place of 80 parts of the unsaturated polyester resin and 20 parts of the 30% styrene dispersion used in Examples 2-5. The resulting resin concrete compositions were cured to produce resin concretes. The obtained results are shown in the following Table 3.
TABLE 3 Results of evaluation of resin concrete*
UPRIA Surface Shrinkage JPR/A Surface Shrinkage (weight ratio) I state (%) Example 6 95/5 o 0.06 Example 7 85/15 o 0.05 Example 8 1 70/30 0 -0.01 Note: * The mark of surface state has the same meaning as that in Table 2.
It can be seen from Table 3 that the resin concrete produced by using the block copolymer mixture of the present invention is good in the surface state and can be adjusted its property within the range of from low shrinkage to nonshrinkage by changing the addition amount of the block copolymer mixture, and has excellent dimensional stability.

Claims (2)

1. A low shrinking resin mortar composition or resin concrete composition comprising a low shrinking resin consisting of (a) a block copolymer mixture, (b) an unsaturated polyester and (c) a monomer copolymerizable with the unsaturated polyester, said low shrinking resin being used as a binder, and (d) a filler and/or an aggregate, said block copolymer mixture being obtained by firstly polymerizing one of the following monomers (i) and (ii), (i) 10-90 parts by weight of a monomer consisting of 70100% by weight of vinyl acetate and 300% by weight of a monomer copolymerizable with vinyl acetate, and (ii) 90-1 0 parts by weight of a monomer consisting of 0-1 00% by weight of a styrene series monomer and 1 00-0% by weight of an acrylic acid ester and/or a methacrylic acid ester, in the presence of a polymerization initiator of a polymeric peroxide having the following general formula
wherein R, represents an alkylene group or substituted alkylene group having 1-18 carbon atoms, a cycloalkylene group or substituted cycloalkylene group having 3-1 5 carbon atoms, or a phenylene group or substituted phenylene group; ; R2 represents an alkylene group or substituted alkylene group having 2-10 carbon atoms,
(wherein R3 represents a hydrogen atom or a methyl group, R4 represents an alkylene group or substituted alkylene group having 2-10 carbon atoms, and m represents an integer of 1-13),
n represents an integer of 2-20, to form a mixture of a copolymer having peroxy bonds in the molecule, and then copolymerizing the copolymer mixture with another monomer.
2. A composition according to claim 1, wherein the binder contains 1-20% by weight of the block copolymer mixture.
GB8133202A 1980-11-08 1981-11-04 Low shrinking resin mortar or resin concrete composition Withdrawn GB2087416A (en)

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JP15644680A JPS5780413A (en) 1980-11-08 1980-11-08 Low-shrinking resin mortar or resin concrete composition

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180344A2 (en) * 1984-10-29 1986-05-07 Nippon Oil And Fats Company, Limited Cured unsaturated polyester resin or vinyl ester resin containing fluorine-containing groups oriented on its surface
US5082878A (en) * 1988-04-15 1992-01-21 W.R. Grace & Co.-Conn Shrink controlled low-temperature-curable polyester resin compositions
DE102008054482A1 (en) 2008-12-10 2010-06-17 Wacker Chemie Ag Graft copolymers and their use as low-profile additives

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57164114A (en) * 1981-04-01 1982-10-08 Nippon Oil & Fats Co Ltd Low-shrinkage unsaturated polyester resin composition
JPS60104299A (en) * 1983-11-10 1985-06-08 株式会社富士電機総合研究所 Method of solidifying radioactive waste
JPS61152714A (en) * 1984-12-26 1986-07-11 Ube Saikon Kk Thermoplastic elastomer resin and production thereof
US5700557A (en) * 1996-12-05 1997-12-23 Lin; Li-Ching Unsaturated polyester and the manufacturing method thereof
CN117661366B (en) * 2024-01-19 2024-06-07 广东捷丰实业投资有限公司 Preparation process of high-strength waterproof composite corrugated paper

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5580423A (en) * 1978-12-13 1980-06-17 Hitachi Chem Co Ltd Low shrinkage unsaturated polyester resin composition
JPS603327B2 (en) * 1979-11-30 1985-01-28 日本油脂株式会社 Low shrinkage unsaturated polyester resin composition
JPS603327A (en) * 1983-06-20 1985-01-09 株式会社イナックス Goose-neck emitting pipe

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180344A2 (en) * 1984-10-29 1986-05-07 Nippon Oil And Fats Company, Limited Cured unsaturated polyester resin or vinyl ester resin containing fluorine-containing groups oriented on its surface
EP0180344A3 (en) * 1984-10-29 1987-10-14 Nippon Oil And Fats Company, Limited Cured unsaturated polyester resin or vinyl ester resin containing fluorine-containing groups oriented on its surface
US5082878A (en) * 1988-04-15 1992-01-21 W.R. Grace & Co.-Conn Shrink controlled low-temperature-curable polyester resin compositions
DE102008054482A1 (en) 2008-12-10 2010-06-17 Wacker Chemie Ag Graft copolymers and their use as low-profile additives
US8952096B2 (en) 2008-12-10 2015-02-10 Wacker Chemie Ag Graft copolymers and use thereof as low-profile additives

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NL8105037A (en) 1982-06-01
JPS5780413A (en) 1982-05-20
DE3143155A1 (en) 1982-05-19

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