CA2322899C - Method of producing polyetherester monomer and cement dispersants - Google Patents
Method of producing polyetherester monomer and cement dispersants Download PDFInfo
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Abstract
Polyetherester monomer of the kind (see above formula) where R1, R2 and R3 are each a group of a specified kind and A is a residual group of another specified kind is produced by an esterification reaction of polyalkyleneglycol with a closed end and unsaturated carboxylic acid, each of a specified kind, by using an acid catalyst under a heated and reduced-pressure condition in the absence of solvents and in the presence of a specified amount of p-benzoquinone and/or phenothiazine. Cement dispersants with improved properties are obtained from water-soluble vinyl monomers produced by using the polyetherester monomer thus obtained as intermediate product.
Description
IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
APPLICATION FOR PATENT
METHOD OF PRODUCING POLYETHERESTER MONOMER AND
CEMENT DISPERSANTS
Inventors: Mitsuo Kinoshita Kazuhisa Okada Background of the Invention This inverition relates to a method of producing polyetherester monomer and cement dispersion agents (or cement dispersants). It has been known to produce polyetherester monomer as an intermediate product by an esterification reaction of polyalkyleneglycol with a closed end and unsaturated carboxylic acid and to copolymerize this polyetherester monomer with vinyl monomers which are copolymerizable therewith to obtain vinyl copolymers that can be used widely as a dispersant, an antistatic agent, an antifogging agent, an emulsifier or an adherent. In such applications, the quality of the monomer to be used in suctr a copolyinerization reaction, and in particular the quality of polyetherester monomer, is known to significantly affect the quality of the produced vinyl copolymer serving as a dispersant, an antistatic an antifogging agent, an enuilsifier or an adherent. In other words, if the quality of polyetherester monomer obitained as the intermediate product is not sufficiently high, vinyl c.opolycners produced therefrom cannot function satisfactorily as a dispersant, an antistatic agent, an antifogging agent, an emulsifier or an adherent.
U. S. Patents 4,962,173 and 5,362,829, for example, disclosed water-soluble vinyl copolynriers having polyalkyleneglycol chain as a side chain serving as cement dispersants capable of providing a superior fluidity characteristic with a small slump loss to hydraulic cement compositions such as mortar and concrete. Such a water-soluble vinyl copolymer is usually produced by first preparing polyetherester monoiner as an intermediate product by an esterification reaction of polyalkyleneglycol with a closed end and unsaturated carboxylic acid and therr copolymerizing it with vinyl monomers capable oi.' copolymerizing therewith. In this case, the quality as a cement dispersant of the water-soluble vinyl copolymer which is obtained is significantly dependent on the quality of the monomer, and in particular that of polyetherester monomer, that is used in the copolymerization reaction. In other words, if the polyetherester monomer serving as an intermediate product is of a poor quality, fluidity cannot be provided to a satisfactory manner to a hydraulic cement composition when the water-soluble vinyl copolymer obtained therefrom is used as a cement dispersant.
The fluidity which has been provided has a large slump loss in such a case, and products obtained by hardening sucli a hydraulic cement composition have a low compressive strength.
As disclosed in Japanese Patent Publication Tokkai 11-71151, such polyetherester monomers as described above have conventionally been produced by using an organic solvent witli a low boiling point such as benzene in an esterification reaction oi`' polyalkyleneglycol with a closed end and unsaturated carboxylic acid. Use of such an organic solvent with a low boiling point is advantageous in that it is possible to obtain polyetheresters of a fairly high quality. On the other hand., the solvent which has been used for the reactiorr must be collecteci and thP. :,t oi'equipment therefor adds to the total production cost of the polyetherester, or that of the vinyl copolymer to be used as the intermediate product and tl-iat of the water-soluble vinyl copolymers serving as a cement dispersant. In addition, the workers will be forced to work in an undesirable environment due to some of the properties of these substances.
Summary of the Invention It is therefore an object of tliis invention to pi-ovide a method of producing polyetherester monomer of a high quality without using a solvent.
It is anothe;r object of this invention to provide water-soluble vinyl copolymers capable of serving as a cement dispersant with improved properties, obtainable from such polyetherester monomer.
The present inventors discovered, as a result of work in view of the above objects, firstly that polyetherester monomer of a high quality can be obtained by an esterification reaction of polyalkyleneglycol with a closed end and unsaturated carboxylic acicl under a specified condition in the presence of a specified amount of p-benzoquinone and/or phenothiazine and in the absence of any solvent, and secondly that water-soluble vinyl copolymers obtained by a radical copolymerization reactiori of this polyetherester monomer with vinyl monomers which are copolynlerizable therewith in an aqueous solution have improved properties as a cement dispersant.
Detailed Description of the Invention This inverition relates, on one hand, to a method of producing polyetherester monomer shown by Formula 3 given below, by causing an esterification reaction of polyalkyleneglycol with a closed end shown by Formula 1 given below and unsaturated carboxylic acid shown by Formula 2 given below by using an acid catalyst under a heated and reduced-pressure condition in the absence of solvents and in the presence of p-benzoquinone and/or phenothiazine in an amourit of 0.03-0.5 weiglit % of polyalkyleneglycol with a closed ci,u while distilling away generated water, where Formulas 1, 2 and 3 are respectively:
R3-()-A-OH (Formula 1) R' R2 I 1 (Formula 2) CH==C-COOH
R' R' CH=C (Formiula 3) N
where Rl and RZ are each I-1 oi- methyl group, R3 is alkyl group with 1-22 carbon atoms, benzyl group, phenyl group or alkylphenyl group having alkyl group with 1-12 carbon atoms, and A is residual group obtained by removing all hydroxyl groups from polyalkyleneglycol of which the repetition number of oxyalkylene units (consisting either only of oxyethylene units or of both oxyethylene units and oxypropylene units) being 5-250. This invention relates, on the other hand, to cement dispersants characterized as comprising water-soluble vinyl copolymer obtained by a radical copolymerization reaction of polyetherester monomer produced by a method described above and vinyl monomers that can be copolymerized therewith.
According to this invention, explained more in detail, polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Formula 2 are caused to undergo an esterification reaction in the absence of a solvent to obtain polyetherester monomer shown by Formula 3. Examples of W in Formula 1 for polyalkyleneglycol with a closed end include (1) alkyl groups with 1-22 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl gi-oup arid docosanyl group; (2) benzyl group; (3) phenyl group; and (4) alkylphenyl groups having aiKA- group with 1-12 carbon atoms such as methylphenyl group, ethylplhenyl group, propylphenyl group, isopropylphenyl group, butylphenyl group, htexylphenyl group, octylphenyl group, nonylphenyl group and dodecylphenvl gi-oup. Among these, however, alkyl groups with 1-12 carbon atoms and benzyl group are preferable and alkyl groups with 1-3 carbon atoms are even more preferable.
As for A in Formulas 1 and 3, examples thereof include (1) residual groups obtained :)y removing all hydroxyl groups from polyethyleneglycol of which the oxyalkylene units are all oxyethylene units and (2) residual groups obtair:eci by removing all hydroxyl groups from polyethylene-polypropyleneglycol of which the oxyalkylene units include both oxyethylene units and oxypropylene units, but residual groups obtained by removing all hydroxyl groups from polyethyleneglycol are preferred. If residual groups obtained by removing all hydroxyl groups from polyethylene-polypropyleneglycol are used as A, the repetition of its oxyethylene and oxypropylene units may be by 5 random and/or block connections. The repetition number of the oxyalkyletie units in the residual group representing A is 5-250, and is preferably 7-90.
Examples of polyalkyleneglycol with a closed end shown by Formula 1 include methoxy polyethyleneglycol, methoxy polyethyleneglycol-polypropyleneglycol, ethoxy polyethyleneglycol, ethoxy polyethyleneglycol-polypropyleneglycol, propoxy polyethyleneglycol, propoxy polyethyleneglycol-polypropyleneglycol, butoxy polyethyleneglycol, lauryloxy polyethyleneglycol, butoxy polyethyleneglycol-polypropyleneglycol, benzyloxy polyethyleneglycol, benzyloxy polyethyleneglycol-polypropyleneglycol, phenoxy polyethyleneglycol, phenoxy polyethyleneglycol-polypropyleneglycol, alkylphenoxy polyethyleneglycol, and alkylphenoxy polyethyleneglycol-polypropyleneglycol.
Examples of unsaturated carboxylic acid shown by Formula 2 include methacrylic acid, acrylic acid and crotonic acid. Among these, methacrylic acid is desirable.
According to this invention, polyetherester monomer shown by Formula 3 is obtained by causing polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Formula 2 as explained above to undergo an esterification reaction by using an acid catalyst under a heated and reduced-pressure condition in the absence of solvents and in the presence of p-benzoquinone and/or phenothiazine while distilling away generated water. The amount of p-benz.oquinone and/or phenothiazine to be present in this reacting system should be 0.03-0.5 weight %, and preferably 0.1-0.25 weight %, of polyalkyleneglycol with a closed end shown by Formula 1. In particular, the presence of p-benzoquinone in an amount of 0.1-0.25 weight % of polyalkyleneglycol with a closed end shown by Formula 1 is preferable. If the amount of p-benzoquinone and/or plienotlliazine present in the reacting system is less than 0.03 weight % of polyalkyleneglycol with a closed end shown by Formula 1, there is not sufficient effect of preventing polymerization. If it is greater than 0.5 weight %, on the other hand, the effect of preventing polymerization is sufficient but the radical copolymerization reaction does not proceed smoothly when the polyetherester monomer thus obtained is used as an intermediate product to produce vinyl copolymers.
The heatino; at the time of the aforementioned esterification reaction should preferably be to the temperature range of 105-135 C and the pressure in the range of 15-0.5kPa. The heating and the lowering of the pressure should preferably be carried out either continuously or in a stepwise manner within the ranges given above.
Examples of the acid catalyst to be used in the esterification reaction include sulfuric acid, p-toluene sulfonic acid, phosphoric acid and methane sulfonic acid. They may be used either singly or as a mixture but it is preferable to use sulfuric acid singly or a mixed acid of sulfuric acid and p-toluene sulfonic acid. The amount of the acid catalyst to be used is preferably 0.2-1.5 weight % of the total of polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Forinula 2.
The ratio between the amounts of polyalkyleneglycol with a closed end shown by Forinula I and unsaturated carboxylic acid shown by Formula 2 to be used in the esterification reaction should preferably be 1/1.5-(in molar ratio). After the esterific~-::., reaction, the excess portion of unsaturated carboxylic acid is distilled away.
The method of'producing polyetherester monomer according to this invention is explained next further in detail. When methoxy polyethyleneglycol methacrylate, for example, is produced as the polyetherester monomer of this i-ivention, methoxy polyethyleneglycol and an excess amount of methacrylic acid ai-e placed inside a reactor and a specified ainount of p-benzoquinone and/or phenothiazine serving as a polymerization inhibitor, appropriate for the amount of the methoxy polyethyleneglycol and a specified amount of concentrated sulf'uric acid serving as an acid catalyst are added into the reactor. Next, the temperature of the reactin; system is gradually raised and its pressure is gradually lowered until a specified temperature-pressure condition is reached. An esterification reaction is carried out under this temperature-pressure condition while water wliich is generated is removed by azeotropic distillation of water and methacrylic acid. After the esterification reaction, the excess portion of methacrylic acid is removed to obtain methoxy polyethyleneglycol methacrylate. The polyetli erester monomer thus obtained contains the aforementioned polymerization inhibitor and acid catalyst but it may be directly used as an intermediate product for the production of vinyl copolymers without refining to remove them.
Next, cement dispersants according to this invention will be described. The cernent dispersants of this invention are characterized as comprising water-soluble vinyl copolymers obtained through the following two steps, the first step being that of obtaining polyetherester monomer shown by Formula 3 as described above, that is, by causing an esterification reaction of polyalkyleneglycol with a closed end shown by Formula I and unsaturated carboxylic acid shown by Forrnula 2 by using an acid catalyst under a heated and reduced-pressure condition in the absence of solvents and in the presence of'p-benzoquinone and/or phenothiazine in an arnount of 0.03-0.5 weight % of the polyalkyleneglycol with a closed end while distilling away generated water, and the second step being that of obtaining water-soluble vinyl copolymers by a radical copolymerization reaction of the polyetllerester monomer obtained in the first step with vinyl monomers which are copolymerizable with it inside an aqueous solution.
Any of known kinds of vinyl monorners can be used in the second step as long as they are copolymerizable with polyetherester monomer. Examples of such vinyl monomer inclu.de, ethylenic unsaturated monocarboxylic acids and/or their salts, ethylenic unsaturated dicarboxylic acids and/or their salts, ethylenic unsaturated monocarboxylic acid esters, unsaturated carboxylic acid esters witli hiydroxyl group, aromatic vinyl nionomers, vinyl monomers with amino group, vinyl monorners with amide group, vinyl monomers with aldehyde group, vinyl monomers with riitrile group, vinyl esters, alkene compounds, dien compounds and vinyl monomers having sulfonic acid group. Among these, ethylenic unsaturated monocarboxylic acids and/or their salts and vinyl monomers with sulfonic acid group are desirable. Particularly preferable are (1) (meth)acrylic acids and/or their salts sucli as (meth)acrylic acid, alkali metal salts of (meth)acrylic acid, alkali earth metal salts of (meth)acrylic acid and orgar-ic amine salts of (meth)acrylic acid, and (2) methallyl sulfonic acid salts to be used with such (meth)acrylic acids and/or their salts such as alkali metal salts of methallyl sulfonic acid, alkali earth metal salts of methallyl sulfonic acid and organic amine salts of methallyl sulfonic acid.
The invention does not impose any particular limitation on the copolymerization ratios of polyetherester monomer and vinyl monomers which are copolynierizable therewith but in the case of radical copolymerization of' polyetherester monomer and (meth)acrylic acid and/or its salt, it is preferable to copolymerize 5-50 molar % of polyetherester monomer with 50-95 molar % of (meth)acrylic acid and/or its salt (such that the total will be 100 molar %), while in the case of radical copolymerization of polyetherester monomer, (meth)acrylic acid and/or its salt and methallyl sulfonic acid salt, it is preferable to copolymerize 5-45 molar % of polyetherester monomer, 50-90 molar % of (meth)acrylic acid and/or its salt and 0.3-15 molar % of inethallyl sulfonic acid (such that the total will be 100 molar %).
The radical c.opolymerizatior: ::;u, tion itself can be carried out in a known manner sucli as described, for example, in Japanese Patent Publication Tokkai 8-290948. Water-soluble vinyl copolymer can be obtained, for example, by preparing an aqueous solution containing polyetherester monomer obtained in the first step, vinyl monorners which are copolymerizable therewith and a chain transfer agent and causinL; a radical copolymerization i-eaction for 4-8 hours at reaction temperature of 5O-90 C in a nitrogen environment by adding a radical initiator. Examples of chain transfer agent which inay be used in this process include 2-mercaptoethanol, mercaptopropionic acid and mercaptoacetic acid.
Examples of radical initiator include persulfates such as sodium persulfate, potassium persulfate and ai-nmonium persulfate and water-soluble radical initiators such as 2,2'-azobis(2-amidinopropane) dihydrochloride.
The average numerical molecular weight (hereinafter Pullulan converted by GPC method) of the water-soluble vinyl copolymers thus obtained by radical copolymerization is preferably 3500-70000 and more preferably 5000-40000.
Cement dispersants embodying this invention which comprises the water-soluble vinyl copolymers may be used for many kinds of hydraulic cecnent compositions using not only cement but also a mixing material in a fine powder form as a binder, or mortar and concrete as typical examples. Examples of cement include different kinds of portland cement such as normal portland cement, high early portland cement and moderate heat portland cement, as well as many different kinds of blended cement such as portland blast-furnace slag cement, fly ash cement and silica pozzolan cement. Examples of mixing material in a fine powder form inclucie lime stone powder, calcium carbonate, silica fume, blast-furnace slag powder and fly ash.
The rate at which the cement dispersants of this invention should be used is normally 0.01-2.5 weight parts and preferably 0.05-1.5 weight parts %
(by solid component) for 100 weight parts of binder consisting of cement or cement and mixing powder material.
The method of producing polyetherester monomer embodying this invention is characterized in that no solvent is used in the esterification reaction of polyalkyleneglycol with a closed end shown by Formula 1 and unsaturateci carboxylic acid shown by Formula 2. As an important result of this, there is no need to collect any solvent after the esterification reaction is completed.
Moreover, the method of this invention is capable of producing polyetherester monomer of' a high quality shown by Formula 3. As will be described in detail below, polyetherester monomer with high esterification reaction rate can be obtained witllout abnornlal increase in viscosity or generation of gel at the time of the esterification reaction. Water-soluble vinyl copolymers using high-quality polyetherester monorner produced by a method of this invention as an intermediate product exhibit desirable characteristics as cement dispersant.
They can provide fluidity to hydraulic cement compositions with only a small slump loss and hardened products obtained from such hydraulic cement coampositions have improved compressive strength.
5 The inverition is described next by way of the following seven ((1)-(7)) examples of inetliod embodying the invention.
(1) Method of obtaining polyetherester monomer (P-1) without using a solvent by causing esterification reaction with 1.0 mole of methoxy polyethyleneglycol (with repetition number of oxyethylene units equal to 10 9, hereinafter written as n=9) and 2.0 moles of methacrylic acid in the presence of p-benzoquinone in an amount corresponding to 0.21 weight % of this methoxy polyethyleneglycol (n=9) under the condition of temperature 125-130 C and pressure 12-2.5kPa and by using sulfuric acid as catalyst in an amount corresponding to 0.23 weight % of tiie total of methoxy polyethyleneglycol (n=9) and methacrylic acid while reinoving generated water by distillation and thereafter removing the excess amount of metliacrylic acid by distillation.
(2) Metltod of obtaining polyetherester monomer (P-2) without using a solvent by causing esterification reaction with 1.0 mole of methoxy polyethyleneglycol (n=23) and 3.5 moles of methacrylic acid in the presence of p-benzoquinone in an amount corresponding to 0.18 weight % of this methoxy polyethyleneglycol (n==23) under the conditl.,,i of temperature 125-130 C and pressure 10-2.51cPa and by using sulfuric acid as catalyst in an amount corresponding to 0.49 weight % of the total of methoxy polyethyleneglycol (n=23) and methacrylic acid while removing generated water by distillation and thereafter removing the excess amount of inethacrylic acid by distillation.
APPLICATION FOR PATENT
METHOD OF PRODUCING POLYETHERESTER MONOMER AND
CEMENT DISPERSANTS
Inventors: Mitsuo Kinoshita Kazuhisa Okada Background of the Invention This inverition relates to a method of producing polyetherester monomer and cement dispersion agents (or cement dispersants). It has been known to produce polyetherester monomer as an intermediate product by an esterification reaction of polyalkyleneglycol with a closed end and unsaturated carboxylic acid and to copolymerize this polyetherester monomer with vinyl monomers which are copolymerizable therewith to obtain vinyl copolymers that can be used widely as a dispersant, an antistatic agent, an antifogging agent, an emulsifier or an adherent. In such applications, the quality of the monomer to be used in suctr a copolyinerization reaction, and in particular the quality of polyetherester monomer, is known to significantly affect the quality of the produced vinyl copolymer serving as a dispersant, an antistatic an antifogging agent, an enuilsifier or an adherent. In other words, if the quality of polyetherester monomer obitained as the intermediate product is not sufficiently high, vinyl c.opolycners produced therefrom cannot function satisfactorily as a dispersant, an antistatic agent, an antifogging agent, an emulsifier or an adherent.
U. S. Patents 4,962,173 and 5,362,829, for example, disclosed water-soluble vinyl copolynriers having polyalkyleneglycol chain as a side chain serving as cement dispersants capable of providing a superior fluidity characteristic with a small slump loss to hydraulic cement compositions such as mortar and concrete. Such a water-soluble vinyl copolymer is usually produced by first preparing polyetherester monoiner as an intermediate product by an esterification reaction of polyalkyleneglycol with a closed end and unsaturated carboxylic acid and therr copolymerizing it with vinyl monomers capable oi.' copolymerizing therewith. In this case, the quality as a cement dispersant of the water-soluble vinyl copolymer which is obtained is significantly dependent on the quality of the monomer, and in particular that of polyetherester monomer, that is used in the copolymerization reaction. In other words, if the polyetherester monomer serving as an intermediate product is of a poor quality, fluidity cannot be provided to a satisfactory manner to a hydraulic cement composition when the water-soluble vinyl copolymer obtained therefrom is used as a cement dispersant.
The fluidity which has been provided has a large slump loss in such a case, and products obtained by hardening sucli a hydraulic cement composition have a low compressive strength.
As disclosed in Japanese Patent Publication Tokkai 11-71151, such polyetherester monomers as described above have conventionally been produced by using an organic solvent witli a low boiling point such as benzene in an esterification reaction oi`' polyalkyleneglycol with a closed end and unsaturated carboxylic acid. Use of such an organic solvent with a low boiling point is advantageous in that it is possible to obtain polyetheresters of a fairly high quality. On the other hand., the solvent which has been used for the reactiorr must be collecteci and thP. :,t oi'equipment therefor adds to the total production cost of the polyetherester, or that of the vinyl copolymer to be used as the intermediate product and tl-iat of the water-soluble vinyl copolymers serving as a cement dispersant. In addition, the workers will be forced to work in an undesirable environment due to some of the properties of these substances.
Summary of the Invention It is therefore an object of tliis invention to pi-ovide a method of producing polyetherester monomer of a high quality without using a solvent.
It is anothe;r object of this invention to provide water-soluble vinyl copolymers capable of serving as a cement dispersant with improved properties, obtainable from such polyetherester monomer.
The present inventors discovered, as a result of work in view of the above objects, firstly that polyetherester monomer of a high quality can be obtained by an esterification reaction of polyalkyleneglycol with a closed end and unsaturated carboxylic acicl under a specified condition in the presence of a specified amount of p-benzoquinone and/or phenothiazine and in the absence of any solvent, and secondly that water-soluble vinyl copolymers obtained by a radical copolymerization reactiori of this polyetherester monomer with vinyl monomers which are copolynlerizable therewith in an aqueous solution have improved properties as a cement dispersant.
Detailed Description of the Invention This inverition relates, on one hand, to a method of producing polyetherester monomer shown by Formula 3 given below, by causing an esterification reaction of polyalkyleneglycol with a closed end shown by Formula 1 given below and unsaturated carboxylic acid shown by Formula 2 given below by using an acid catalyst under a heated and reduced-pressure condition in the absence of solvents and in the presence of p-benzoquinone and/or phenothiazine in an amourit of 0.03-0.5 weiglit % of polyalkyleneglycol with a closed ci,u while distilling away generated water, where Formulas 1, 2 and 3 are respectively:
R3-()-A-OH (Formula 1) R' R2 I 1 (Formula 2) CH==C-COOH
R' R' CH=C (Formiula 3) N
where Rl and RZ are each I-1 oi- methyl group, R3 is alkyl group with 1-22 carbon atoms, benzyl group, phenyl group or alkylphenyl group having alkyl group with 1-12 carbon atoms, and A is residual group obtained by removing all hydroxyl groups from polyalkyleneglycol of which the repetition number of oxyalkylene units (consisting either only of oxyethylene units or of both oxyethylene units and oxypropylene units) being 5-250. This invention relates, on the other hand, to cement dispersants characterized as comprising water-soluble vinyl copolymer obtained by a radical copolymerization reaction of polyetherester monomer produced by a method described above and vinyl monomers that can be copolymerized therewith.
According to this invention, explained more in detail, polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Formula 2 are caused to undergo an esterification reaction in the absence of a solvent to obtain polyetherester monomer shown by Formula 3. Examples of W in Formula 1 for polyalkyleneglycol with a closed end include (1) alkyl groups with 1-22 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl gi-oup arid docosanyl group; (2) benzyl group; (3) phenyl group; and (4) alkylphenyl groups having aiKA- group with 1-12 carbon atoms such as methylphenyl group, ethylplhenyl group, propylphenyl group, isopropylphenyl group, butylphenyl group, htexylphenyl group, octylphenyl group, nonylphenyl group and dodecylphenvl gi-oup. Among these, however, alkyl groups with 1-12 carbon atoms and benzyl group are preferable and alkyl groups with 1-3 carbon atoms are even more preferable.
As for A in Formulas 1 and 3, examples thereof include (1) residual groups obtained :)y removing all hydroxyl groups from polyethyleneglycol of which the oxyalkylene units are all oxyethylene units and (2) residual groups obtair:eci by removing all hydroxyl groups from polyethylene-polypropyleneglycol of which the oxyalkylene units include both oxyethylene units and oxypropylene units, but residual groups obtained by removing all hydroxyl groups from polyethyleneglycol are preferred. If residual groups obtained by removing all hydroxyl groups from polyethylene-polypropyleneglycol are used as A, the repetition of its oxyethylene and oxypropylene units may be by 5 random and/or block connections. The repetition number of the oxyalkyletie units in the residual group representing A is 5-250, and is preferably 7-90.
Examples of polyalkyleneglycol with a closed end shown by Formula 1 include methoxy polyethyleneglycol, methoxy polyethyleneglycol-polypropyleneglycol, ethoxy polyethyleneglycol, ethoxy polyethyleneglycol-polypropyleneglycol, propoxy polyethyleneglycol, propoxy polyethyleneglycol-polypropyleneglycol, butoxy polyethyleneglycol, lauryloxy polyethyleneglycol, butoxy polyethyleneglycol-polypropyleneglycol, benzyloxy polyethyleneglycol, benzyloxy polyethyleneglycol-polypropyleneglycol, phenoxy polyethyleneglycol, phenoxy polyethyleneglycol-polypropyleneglycol, alkylphenoxy polyethyleneglycol, and alkylphenoxy polyethyleneglycol-polypropyleneglycol.
Examples of unsaturated carboxylic acid shown by Formula 2 include methacrylic acid, acrylic acid and crotonic acid. Among these, methacrylic acid is desirable.
According to this invention, polyetherester monomer shown by Formula 3 is obtained by causing polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Formula 2 as explained above to undergo an esterification reaction by using an acid catalyst under a heated and reduced-pressure condition in the absence of solvents and in the presence of p-benzoquinone and/or phenothiazine while distilling away generated water. The amount of p-benz.oquinone and/or phenothiazine to be present in this reacting system should be 0.03-0.5 weight %, and preferably 0.1-0.25 weight %, of polyalkyleneglycol with a closed end shown by Formula 1. In particular, the presence of p-benzoquinone in an amount of 0.1-0.25 weight % of polyalkyleneglycol with a closed end shown by Formula 1 is preferable. If the amount of p-benzoquinone and/or plienotlliazine present in the reacting system is less than 0.03 weight % of polyalkyleneglycol with a closed end shown by Formula 1, there is not sufficient effect of preventing polymerization. If it is greater than 0.5 weight %, on the other hand, the effect of preventing polymerization is sufficient but the radical copolymerization reaction does not proceed smoothly when the polyetherester monomer thus obtained is used as an intermediate product to produce vinyl copolymers.
The heatino; at the time of the aforementioned esterification reaction should preferably be to the temperature range of 105-135 C and the pressure in the range of 15-0.5kPa. The heating and the lowering of the pressure should preferably be carried out either continuously or in a stepwise manner within the ranges given above.
Examples of the acid catalyst to be used in the esterification reaction include sulfuric acid, p-toluene sulfonic acid, phosphoric acid and methane sulfonic acid. They may be used either singly or as a mixture but it is preferable to use sulfuric acid singly or a mixed acid of sulfuric acid and p-toluene sulfonic acid. The amount of the acid catalyst to be used is preferably 0.2-1.5 weight % of the total of polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Forinula 2.
The ratio between the amounts of polyalkyleneglycol with a closed end shown by Forinula I and unsaturated carboxylic acid shown by Formula 2 to be used in the esterification reaction should preferably be 1/1.5-(in molar ratio). After the esterific~-::., reaction, the excess portion of unsaturated carboxylic acid is distilled away.
The method of'producing polyetherester monomer according to this invention is explained next further in detail. When methoxy polyethyleneglycol methacrylate, for example, is produced as the polyetherester monomer of this i-ivention, methoxy polyethyleneglycol and an excess amount of methacrylic acid ai-e placed inside a reactor and a specified ainount of p-benzoquinone and/or phenothiazine serving as a polymerization inhibitor, appropriate for the amount of the methoxy polyethyleneglycol and a specified amount of concentrated sulf'uric acid serving as an acid catalyst are added into the reactor. Next, the temperature of the reactin; system is gradually raised and its pressure is gradually lowered until a specified temperature-pressure condition is reached. An esterification reaction is carried out under this temperature-pressure condition while water wliich is generated is removed by azeotropic distillation of water and methacrylic acid. After the esterification reaction, the excess portion of methacrylic acid is removed to obtain methoxy polyethyleneglycol methacrylate. The polyetli erester monomer thus obtained contains the aforementioned polymerization inhibitor and acid catalyst but it may be directly used as an intermediate product for the production of vinyl copolymers without refining to remove them.
Next, cement dispersants according to this invention will be described. The cernent dispersants of this invention are characterized as comprising water-soluble vinyl copolymers obtained through the following two steps, the first step being that of obtaining polyetherester monomer shown by Formula 3 as described above, that is, by causing an esterification reaction of polyalkyleneglycol with a closed end shown by Formula I and unsaturated carboxylic acid shown by Forrnula 2 by using an acid catalyst under a heated and reduced-pressure condition in the absence of solvents and in the presence of'p-benzoquinone and/or phenothiazine in an arnount of 0.03-0.5 weight % of the polyalkyleneglycol with a closed end while distilling away generated water, and the second step being that of obtaining water-soluble vinyl copolymers by a radical copolymerization reaction of the polyetllerester monomer obtained in the first step with vinyl monomers which are copolymerizable with it inside an aqueous solution.
Any of known kinds of vinyl monorners can be used in the second step as long as they are copolymerizable with polyetherester monomer. Examples of such vinyl monomer inclu.de, ethylenic unsaturated monocarboxylic acids and/or their salts, ethylenic unsaturated dicarboxylic acids and/or their salts, ethylenic unsaturated monocarboxylic acid esters, unsaturated carboxylic acid esters witli hiydroxyl group, aromatic vinyl nionomers, vinyl monomers with amino group, vinyl monorners with amide group, vinyl monomers with aldehyde group, vinyl monomers with riitrile group, vinyl esters, alkene compounds, dien compounds and vinyl monomers having sulfonic acid group. Among these, ethylenic unsaturated monocarboxylic acids and/or their salts and vinyl monomers with sulfonic acid group are desirable. Particularly preferable are (1) (meth)acrylic acids and/or their salts sucli as (meth)acrylic acid, alkali metal salts of (meth)acrylic acid, alkali earth metal salts of (meth)acrylic acid and orgar-ic amine salts of (meth)acrylic acid, and (2) methallyl sulfonic acid salts to be used with such (meth)acrylic acids and/or their salts such as alkali metal salts of methallyl sulfonic acid, alkali earth metal salts of methallyl sulfonic acid and organic amine salts of methallyl sulfonic acid.
The invention does not impose any particular limitation on the copolymerization ratios of polyetherester monomer and vinyl monomers which are copolynierizable therewith but in the case of radical copolymerization of' polyetherester monomer and (meth)acrylic acid and/or its salt, it is preferable to copolymerize 5-50 molar % of polyetherester monomer with 50-95 molar % of (meth)acrylic acid and/or its salt (such that the total will be 100 molar %), while in the case of radical copolymerization of polyetherester monomer, (meth)acrylic acid and/or its salt and methallyl sulfonic acid salt, it is preferable to copolymerize 5-45 molar % of polyetherester monomer, 50-90 molar % of (meth)acrylic acid and/or its salt and 0.3-15 molar % of inethallyl sulfonic acid (such that the total will be 100 molar %).
The radical c.opolymerizatior: ::;u, tion itself can be carried out in a known manner sucli as described, for example, in Japanese Patent Publication Tokkai 8-290948. Water-soluble vinyl copolymer can be obtained, for example, by preparing an aqueous solution containing polyetherester monomer obtained in the first step, vinyl monorners which are copolymerizable therewith and a chain transfer agent and causinL; a radical copolymerization i-eaction for 4-8 hours at reaction temperature of 5O-90 C in a nitrogen environment by adding a radical initiator. Examples of chain transfer agent which inay be used in this process include 2-mercaptoethanol, mercaptopropionic acid and mercaptoacetic acid.
Examples of radical initiator include persulfates such as sodium persulfate, potassium persulfate and ai-nmonium persulfate and water-soluble radical initiators such as 2,2'-azobis(2-amidinopropane) dihydrochloride.
The average numerical molecular weight (hereinafter Pullulan converted by GPC method) of the water-soluble vinyl copolymers thus obtained by radical copolymerization is preferably 3500-70000 and more preferably 5000-40000.
Cement dispersants embodying this invention which comprises the water-soluble vinyl copolymers may be used for many kinds of hydraulic cecnent compositions using not only cement but also a mixing material in a fine powder form as a binder, or mortar and concrete as typical examples. Examples of cement include different kinds of portland cement such as normal portland cement, high early portland cement and moderate heat portland cement, as well as many different kinds of blended cement such as portland blast-furnace slag cement, fly ash cement and silica pozzolan cement. Examples of mixing material in a fine powder form inclucie lime stone powder, calcium carbonate, silica fume, blast-furnace slag powder and fly ash.
The rate at which the cement dispersants of this invention should be used is normally 0.01-2.5 weight parts and preferably 0.05-1.5 weight parts %
(by solid component) for 100 weight parts of binder consisting of cement or cement and mixing powder material.
The method of producing polyetherester monomer embodying this invention is characterized in that no solvent is used in the esterification reaction of polyalkyleneglycol with a closed end shown by Formula 1 and unsaturateci carboxylic acid shown by Formula 2. As an important result of this, there is no need to collect any solvent after the esterification reaction is completed.
Moreover, the method of this invention is capable of producing polyetherester monomer of' a high quality shown by Formula 3. As will be described in detail below, polyetherester monomer with high esterification reaction rate can be obtained witllout abnornlal increase in viscosity or generation of gel at the time of the esterification reaction. Water-soluble vinyl copolymers using high-quality polyetherester monorner produced by a method of this invention as an intermediate product exhibit desirable characteristics as cement dispersant.
They can provide fluidity to hydraulic cement compositions with only a small slump loss and hardened products obtained from such hydraulic cement coampositions have improved compressive strength.
5 The inverition is described next by way of the following seven ((1)-(7)) examples of inetliod embodying the invention.
(1) Method of obtaining polyetherester monomer (P-1) without using a solvent by causing esterification reaction with 1.0 mole of methoxy polyethyleneglycol (with repetition number of oxyethylene units equal to 10 9, hereinafter written as n=9) and 2.0 moles of methacrylic acid in the presence of p-benzoquinone in an amount corresponding to 0.21 weight % of this methoxy polyethyleneglycol (n=9) under the condition of temperature 125-130 C and pressure 12-2.5kPa and by using sulfuric acid as catalyst in an amount corresponding to 0.23 weight % of tiie total of methoxy polyethyleneglycol (n=9) and methacrylic acid while reinoving generated water by distillation and thereafter removing the excess amount of metliacrylic acid by distillation.
(2) Metltod of obtaining polyetherester monomer (P-2) without using a solvent by causing esterification reaction with 1.0 mole of methoxy polyethyleneglycol (n=23) and 3.5 moles of methacrylic acid in the presence of p-benzoquinone in an amount corresponding to 0.18 weight % of this methoxy polyethyleneglycol (n==23) under the conditl.,,i of temperature 125-130 C and pressure 10-2.51cPa and by using sulfuric acid as catalyst in an amount corresponding to 0.49 weight % of the total of methoxy polyethyleneglycol (n=23) and methacrylic acid while removing generated water by distillation and thereafter removing the excess amount of inethacrylic acid by distillation.
(3) Method of obtaining polyetherester monomer (P-3) without usirig a solvent by causing esteritication reaction with 1.0 mole of methoxy polyethyleneglyc:ol (n=75) and 3.6 moles of inethacrylic acid in the presence of p-benzoquinone in an amount corresponding to 0. 15 weight % of this methoxy polyethyleneglyc:ol (n=75) under the condition of temperature 125-130 C and pressure 7-1.5k11a andby using sulfuric acid as catalyst in an amount corresponding to 0.31 wei;;ht % of the total of methoxy polyethyleneglycol (n=75) and methacrylic acid while removing generated water by distillation and thereafter removing the excess amount of methacrylic acid by distillation.
(4) Method of obtaining polyetherester monomer (P-4) without using a solvent by causing esterification reaction with 1.0 mole of benzyloxy polyethyleneglycol (n=90) and 3.2 moles of methacrylic acid in the presence of p-benzoquinone in an amount corresponding to 0.13 weight % of this benzyloxy polyethyleneglycol (n=90) under the condition of temperature 125-130 C and pressure 5-1.5kPa and by using a mixed liquid of sulfuric acid/p-toluene sulfonic acid = 5/2 (in weiglit ratio) as catalyst in an amount corresponding to 0.68 weight % of the total of benzyloxy polyethyleneglycol (n=90) and methacrylic acici while removing generated water by distillation and thereafter removing the excess ainount of inethacrylic acid by distillation.
(5) Method of obtaining polyetherester monomer (P-5) without using a solvent by causing esterification reaction with 1.0 mole of lauryloxy polyethyleneglycol (n=120) and 5.0 moles of methacrylic acid in the presence of p-benzoquinonc: in an amount corresponding to 0.15 weight % of this lauryloxy polyethyleneglycol (n=120) under the condition of temperature 125-130 C and pressure 5-1.5kPa and by using a mixed liquid of sulfuric acid/p-toluene sulfonic acid = 5.5/2.5 (in weight ratio) as catalyst in an amount correspondi!,,- 0.80 weight % of the total of lauryloxy polyethyleneglycol (n=120) and methacrylic acid while removing generated water by distillation and thereafter removing the excess amount of inethacrylic acid by distillation.
(6) Method of obtaining polyetherester monomer (P-6) without using a solvent by causing esterification reaction with 1.0 mole of methoxy polyethyleneglycol (n=23) and 3.5 moles of methacrylic acid in the presence of phenothiazine in an amount corresponding to 0. 19 weight % of this methoxy polyethyleneglycol (n-23) under the condition of temperature 125-130 C and pressure 10-2.5kPa and by using a mixed liquid of sulfuric acid/p-toluene sulfonic acid = 4.S/2..5 (in weight ratio) as catalyst in an amount corresponding to 0.47 weight % of the total of inethoxy polyethyleneglycol (n=23) and methacrylic acid while removing generated water by distillation and thereafter removing the excess amount of inethacrylic acid by distillation.
(7) Method of obtaining polyetherester monomer. (P-7) without using a solvent by causing esterification reaction with 1.0 mole of methoxy polyethyleneglycol (n=75) and 4.1 moles of methacrylic acid in the presence of a mixture p-berizoquinone/phenothiazine = 50/50 (in weight ratio) in an amount corresponding to 0.16 weight % of this methoxy polyethyleneglycol (n=75) under the condition of temperature 125-130 C and pressure 5-1.5kPa and by using a mixed liquid of sulfuric acid/p-toluene sulfonic acid = 4/3 (in weight ratio) as catalyst in an amount corresponding to 0.54 weight % of the total of methoxy polyethyleneglycol (n=75) and methacrylic acid while removing generated water by distillation and tliereafter removing the excess amount of methacrylic acid by distillation.
Next, the invention is described by way of the following 14 ((8)-(21)) examples of cement dispersant embodying the invention:
Next, the invention is described by way of the following 14 ((8)-(21)) examples of cement dispersant embodying the invention:
(8) Cement dispersant comprising water-soluble vinyl copolymer with average rtlumerical molecular weight of 12500 obtained by radical copolymerization of aforementioned polyetlierester monoiner (P-1) and methacrylic acid at the ratio of 35/65 (in molar %) in an aqueous solution.
(9) Cement dispersant comprising water-soluble vinyl copolymer with average numerical molecular weight of 8800 ~b'.u:.,ed by radical copolymerization of aforementioned polyetherester monomer (P-1), sodium methacrylate and sodium methallyl sulfonate at the ratio of 33/61/6 (in molar %) in an aqueous solution.
(10) Cement dispersant comprisirig water-soluble vinyl copolymer with average numerical molecular weight of 17000 obtained by radical copolymerization of aforementioned polyetlierester monomer (P-2) and methacrylic acid at the ratio of 35/65 (in molar %) in an aqueous solution.
(11) Cement dispersant compi-ising water-soluble vinyl copolymer with average nume.rical molecular weight of 9600 obtained by radical copolymerization of afore.mentioned polyetherester monomer (P-2), sodium methacrylate and sodium methallyl sulfonate at the ratio of 33/61/6 (in molar %) in an aqueous solution.
(12) Cernent dispersant comprising water-soluble vinyl copolymer with average numer-ical molecular weight of 25300 obtained by radical copolymerization of aforementioned polyetherester monomer (P-3) and methacrylic: acid at the ratio of 3 5/65 (in molar %) in an aqueous solution.
(13) Cement dispersant comprising water-soluble vinyl copolymer with average numerical molecular weight of 15500 obtained by radical copolymerization of aforementioned polyetherester monomer (P-3), sodium methacrylate and sodium methallyl sulfonate at the ratio of 33/61/6 (in molar %) in an aqueous solution.
(14) Cement dispersant comprising water-soluble vinyl copolymer with average numerical molecular weight of 31000 obtained by radical copolymerization of aforen-ieritioned polyetherester monomer (P-4) and methacrylic acid at the i-atio of 35/65 (in molar %) in an aqueous solution.
(15) Cement dispersant comprising water-soluble vinyl copolymer with average numerical molecular weight of 18000 obtained by radical copolymerization of aforementioned polyetllerester monomer (P-4), sodium methacrylate and sodium methallyl sulfonate at the ratio of 33/61/6 (in molar %) in an aqueous solution.
(16) Cõitacnt dispersant comprising water-soluble vinyl copolymer with average nui.nerical molecular weight of 37800 obtained by radical copolymerization of aforementioned polyetherester monomer (P-5) and methacrylic acid at the ratio of 35/65 (in molar %) in an aqueous solution.
(17) Cement dispersant cornprising water-soluble vinyl copolymer with average numerical molecular weight of 23600 obtained by radical copolymerization of aforementioned polyetherester monomer (P-5), sodium methacrylate and sodium methallyl sulfonate at the ratio of 33/61/6 (in molar %) in an aqueous solution.
(18) Cement dispersant comprising water-soluble vinyl copolymer with average nuinerical molecular weight of 16200 obtained by radical copolymerization of aforen-ieritioned polyetllerester monomer (P-6) and methacrylic acid at the i-atio of 35/65 (in molar %) in an aqueous solution.
(19) Cement dispersant comprising water-soluble vinyl copolymer with average numerical molecular weight of 10400 obtained by radical copolymerization of aforeni&ntioned polyetherester monomer (P-6), sodium methacrylate and sodium methallyl sulfonate at the ratio of 33/61/6 (in molar %) in an aqueous solution.
(20) Cement dispersant comprising water-soluble vinyl copolymer with average numerical molecular weight of 24000 obtained by radical copolymerization of aforementioned polyetherester monomer (P-7) and methacrylic acid at the ratio of 35/65 (in molar %) in an aqueous solution.
(21) Cement dispersant comprising water-soluble vinyl copolymer with average riurnerical molecular weight of 15000 obtained by radical copolymerization of aforeinentioned polyetherester monomer (P-7), sodium methacrylate and sodium methallyl sulfonate at the ratio of 33/61/6 (in molar.
%) in an aqueous solution.
In what follows, the invention will be described by way of the results of test examples but it goes without saying that the invention is not limited to these examples. In the following, "parts" will niean "weight parts" and "%"
will mean "weight %" unless specifically described to be otherwise.
Part 1: Production of polyetherester monomers Test Example 1(Production of polyetherester monomer (P-1) Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 rnoles), p-benzoquinone 2.2 parts and 98%
concentratecl sulfuric acid (sanie concentrated sulfuric acid hereinafter) 3.5 parts were placed inside a reactor. Temperature was increased gradually while stirring and pressure was lowered. While water being generated in the esterification reaction was removed out of the reacting system by distillation as azeotropic water/methacrylic acid mixture, the esterification reaction was continued for hours under the condition of'temperature at 125-130 C and pressure at 12-2.5kPa. Next, the remainirig excess portion of methacrylic acid was removed by distillation by further reducing the pressure to obtain a product. This product was analyzed and identified. as polyetherester monomer (P-i) with hydroxyl value 5 1.3, carboxyl value 1.2, esterification reaction rate (hereinafter calculated from the hydroxyl value) 99%.
Test Examples 2-7 and Comparison Example 1(Production of polyetherester monomers('-2)_(P-7 and (R- 1)) 10 As in Test Example 1, polyetherester monomers (P-2)-(P-7) as Test Examples 2-7 and polyetherester monomer (R-1) as Comparison Example 1 were produced.
Comparison Exani le 2 (Production of polyetherester monomer (r-1)) 15 Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 moles) and concentrated sulfuric acid 3.5 parts were placed inside a reactor to carry out esterification by raising the temperature while stirring but the reaction was discontinued because a large amount of insoluble gel came to be deposited during the process.
Comparison Exam ple 3 P,-~, -`uction of polyetherester monomer (r-2)) Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 inoles), hydroquinone 2.2 parts and concentrated sulfuric acid 3.5 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stir-ring but the reaction was discontinued because a large amount of insoluble gel came to be deposited about one hour after the start.
ConijL3rison Exam4LI^4(Production ofpolyetherester monomer (r-3)) Nlethoxy polyethyleneglycol (n=9) 1060 parts (2.5 nioles), methacrylic acid 430 parts (5 rnoles), hydroquinone monomethyl ether 3.5 parts and concentrated sulfuric acid 3.5 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring but the reaction was discontinued because a. large amount of insoluble gel came to be deposited about 30 minutes after the start.
Comparison Exarnple 5 (Production of polyetherester monomer (r-4)) Methoxy polyetlryleneglycol (n=23) 1140 parts (1.1 moles), methacrylic acid 340 part:s (3.9 moles), p-benzoquinone 0.3 parts and concentrated sulfuric acici 7.2 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring but the reaction was discontinued because a large amount of insoluble gel came to be deposited about one hour the start.
Comparison Exaniple 6 (Production of polyetherester monomer (r-5)) Methoxy polyethyleneglycol (n=23) 1140 parts (1.1 moles), methacrylic acid 340 parts (3.9 inoles), phenothiazine 0.3 parts and concentrated sulfuric acici 7.2 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring but the reaction was discontinued because a large amount of insoluble gel came to be deposited about one hour the start Coniparison Example 7 Production of polyetherester monomer (T-1)) Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 moles), p-benzoquinone 2.2 parts, concentrated sulfuric acici 3.5 parts and benzene as solvent 1000 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring while removing ge.nerated water by distillation. After the esterification reaction, the excess portion of inethacrylic acid and the benzene used as solvent were removed by bubbling nitro~en to obtain a product. This product was analyzed and identified as polyetherester monomer (T-1) with hydroxyl value 1.3, carboxyl value 1.2, esterification reaction rate 99%.
Data on tlte production of these polyetherester monomers are summarized in Tables 1 and. 2.
Table 1 Examples R' A R' R' PE/ Inhibitor Acid Teinp. Pressure UA Catalyst ( C) (kPa) Test Examples 1 P-1 S-1 A-1 H S--1 1/2.0 I-1(0.21) C-1 (0.23) 125-130 12-2.5 2 P-2 S-1 A-2 H S-=1 1/3.5 I-1(0.18) C-1 (0.49) 125-130 10-:2.5 3 P-3 S-1 A-3 H S-1 1/3.6 I-1(0.15) C-1 (0.31) 125-130 7-1.5 4 P-4 S-2 A-4 H S--1 1/3.2 1-1(0.13) C-2 (0.68) 125-130 5-1.5 5 P-5 S-3 A-5 H S-=1 1/5.0 I-1(0.15) C-3 (0.80) 125-130 5-1.5 6 P-6 S-1 A-2 H S-=1 1/3.5 I-2(0.19) C-4 (0.47) 125-130 10-2.5 7 P-7 S-1 A-3 H S-1 1/4.1 I-3(0.16) C-5 (0.54) 125-130 5-1.5 Com E xamples 1 R-1 S-1 A-1 H S-1 1/2.0 1-1(1.0) C-1 (0.23) 125-130 12-2.5 2 r-1 S-1 A-1 H S-1 1/2.0 --- C-1 (0.23) *1 *1 3 r-2 S-1 A-1 H S-1 1/2.0 i-4(0.21) C-1 (0.23) *1 *1 4 r-3 S-1 A-1 H S-1 1/2.0 i-5(0.33) C-1 (0.23) *1 *1 5 r-4 S-1 A-2 H S-1 1/3.5 1-1(0.02) C-1 (0.49) *1 *1 6 r-5 S-1 A-2 H S-1 1/3.5 1-2(0.02) C-1 (0.49) *1 *1 7 T-1 S-1 A-1 H S-1 1/2.0 1-1(0.21) C-1 (0.23) In Table 1:
"Inhibitor" indicates "Polymerization inhibitor" and shows the kind and the weight % (in parentheses) used witli respect to polyalkyleneglycol with a.
closed end.
"Acid Catalyst" shows the kind and the weight % (in parentheses) used with respect to the total ainount of lkyleneglycol with a closed end and unsaturated carboxylic acid.
"PE/UA" indicates the niolar ratio of polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Formula 2.
*1 indicates that the reaction was discontinued.
S-1: Metllyl group S-2: Benzyl group S-3: Lauryl group A-1: Residual group obtained by renioving all hydroxyl groups from polyethyleneglycol with rf:petition number of oxyethylene groups equal to 9.
A-2: Residual group obtained by removing all hydroxyl groups from polyethyleneglycol with repetition number of oxyethylene groups equal to 23.
A-3: Residual groLip obtained by renloving all hydroxyl groups from polyethyleneglycol with repetition number of oxyethylene groups equal to 75.
A-4: Residual gro:ap obtained by i-emoving all hydroxyl groups from polyethyleneglycol with repetition number of oxyethylene groups equal to 90.
A-5: Residual group obtained by removing all hydroxyl groups from polyethyleneglycol with repetition nuinber of oxyethylene groups equal to 120.
I-1. p-benzoquinone I-2: phenothiazine 1-3: Mixture of p-benzoquinone/phenothiazine = 50/50 as weight ratio i-4: Hydroquinone i-5: Hydroquinone monomethyl ether C-1: 98% concentrated sulfuric acid C-2: Mixed acid witli 98% concentrated sulfuric acid and p-toluene sulfonic acid at weight ratio of 5/2.
C-3: Mixed acid wit1198% concentrated sulfuric acid and p-toluene sulfonic acid at weight ratio of 5.5/2.5.
C-4: Mixed acid with 98% concentrated sulfuric acid and p-toluene sulfonic acid at weight ratio of 4.5/2.5.
C-5: Mixed acid with 98% concentrated sulfuric acid and p-toluene sulfonic acid at weiglit ratio of 4/3.
Table 2 Examples Abnormal Generation Esterification Viscosity of Gel Reaction Ratio Iricrease (%) Test Examples Comparison Examples 2 r-1 B B *2 3 r-2 B B *2 4 r-3 B B *2 5 r-4 B B *2 6 r-5 B B *2 In Table 2:
For the evaluation of pc-esence/absence of abnormal viscosity increase:
A: No abnormal viscosity increase during esterification reaction B: Presence of abnormal viscosity increase during esterifrcation reaction For the evaluation of presence/absence of gel generation:
A: NID ;eneration of inscl,.,'-'e gel during esterification reaction B: Presence of generation of insoluble gel during esterification reaction *:': Esterification reaction ratio not measurable because esterification reaction was discontinued due to abnormal viscosity increase or generation of insoluble gel Part 2: Production of water_soluble vinyl copolxmers as cement dispersants Test Exam le 8 Pi-oduction ofwater-soluble vinyl copolymer (D-1)) Polyetlier ester monomer (P-1), obtained in Part 1, 152 parts (0.306 moles), metliacrylic acicl 56 parts (0.65 moles), 3-mercaptopropionic acid 2.1 part and water 330 parts were added to(yether and the atmosphere was replaced with nitrogen after they were dissolved uniformly by stirring. While the temperature of the reacting system was maintained at 80 C in the nitrogen environment by means of a warm bath, polymerization was started by dropping 20% aqueous solution of'sodiuin persulfate 8 parts. The polymerization reaction 5 was continued for 5 hours and an aqueous solution of water-soluble vinyl copolymer was obtained. This water-soluble vinyl copolymer was analyzed and identified as water-soluble vinyl copolymer (D-1) with average numerical molecular weight of 12500 having 3 5 molar % of component unit derived from polyetherester monomer (P-1) and 65 molar % of component unit derived from 10 methacrylic acid.
Test Example 9 (Production of water-soluble vinyl copolymer D-2'1) Polyetherester monomer (P-1), obtained in Part 1, 150 parts (0.30 moles), methacrylic acid 55 parts (0.64 moles), sodium methallylsulfonate 13 15 parts (0.082 moles), water 330 parts and aqueous solution of sodium hydroxide 80 parts were added together and the atmosphere was replaced with nitrogen after they were dissolved uniformly by stirring. While the temperature of the reacting system was mairrtained at 60 C in the nitrogen environment by means of a warm bath, polymerization was started by dropping 20% aqueous solutiori of 20 sodium persulfate 10 parts. T'he polymerization reaction was continued for hour-, ind 30% aqueous sollution of sodiuin hydroxide was added thereafter for a complete neutralization to obtain an aqueous solution of water-soluble vinyl copolyrner. This water-soluble vinyl copolymer was analyzed and identified as water-soluble vinyl copolymer (D-2) with average numerical molecular weight of 8800 havinix, 33 molar /o of'component unit derived from polyetherester rnonomer (P-1), 61 molar 'o of' component unit derived fr-om methacrylic acid and 6 molar % of component unit derived from sodium methallylsulfonate.
Test Examples 1 U_2l (Pr-oduction of water-soluble vinyl copolymers D-Water-soluble vinyl copolyrners (D-3)-(D-14) were produced as in Test Example 8 or 9. The details are shown in Table 3.
Table 3 Test Water- Ratio of Copolymerization Average Examples Soluble (molar %) Numerical Vinyl Molecular Copolymer a b c d Weight In Table 3:
a: Polyetherester rnonomer/molar %
b: Metliacrylic acid c: Sodium nlethacrylate d: Sodium methallyl sulfonate Cornparison Exam)le 8(Production of water-soluble vinyl copolymer Water-so~uble vinyl copolymer (DR-1) was produced as Comparison Example 8 in the same way as described in Test Example 8 for the production of %vater-soli.rble vinyl copolymer (D-1) except that "polyetherester monomer (P-1) 152 parts" was replaced by "polyetherester monomer (R-1)., obtained in Part 1, 152 parts".
%) in an aqueous solution.
In what follows, the invention will be described by way of the results of test examples but it goes without saying that the invention is not limited to these examples. In the following, "parts" will niean "weight parts" and "%"
will mean "weight %" unless specifically described to be otherwise.
Part 1: Production of polyetherester monomers Test Example 1(Production of polyetherester monomer (P-1) Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 rnoles), p-benzoquinone 2.2 parts and 98%
concentratecl sulfuric acid (sanie concentrated sulfuric acid hereinafter) 3.5 parts were placed inside a reactor. Temperature was increased gradually while stirring and pressure was lowered. While water being generated in the esterification reaction was removed out of the reacting system by distillation as azeotropic water/methacrylic acid mixture, the esterification reaction was continued for hours under the condition of'temperature at 125-130 C and pressure at 12-2.5kPa. Next, the remainirig excess portion of methacrylic acid was removed by distillation by further reducing the pressure to obtain a product. This product was analyzed and identified. as polyetherester monomer (P-i) with hydroxyl value 5 1.3, carboxyl value 1.2, esterification reaction rate (hereinafter calculated from the hydroxyl value) 99%.
Test Examples 2-7 and Comparison Example 1(Production of polyetherester monomers('-2)_(P-7 and (R- 1)) 10 As in Test Example 1, polyetherester monomers (P-2)-(P-7) as Test Examples 2-7 and polyetherester monomer (R-1) as Comparison Example 1 were produced.
Comparison Exani le 2 (Production of polyetherester monomer (r-1)) 15 Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 moles) and concentrated sulfuric acid 3.5 parts were placed inside a reactor to carry out esterification by raising the temperature while stirring but the reaction was discontinued because a large amount of insoluble gel came to be deposited during the process.
Comparison Exam ple 3 P,-~, -`uction of polyetherester monomer (r-2)) Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 inoles), hydroquinone 2.2 parts and concentrated sulfuric acid 3.5 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stir-ring but the reaction was discontinued because a large amount of insoluble gel came to be deposited about one hour after the start.
ConijL3rison Exam4LI^4(Production ofpolyetherester monomer (r-3)) Nlethoxy polyethyleneglycol (n=9) 1060 parts (2.5 nioles), methacrylic acid 430 parts (5 rnoles), hydroquinone monomethyl ether 3.5 parts and concentrated sulfuric acid 3.5 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring but the reaction was discontinued because a. large amount of insoluble gel came to be deposited about 30 minutes after the start.
Comparison Exarnple 5 (Production of polyetherester monomer (r-4)) Methoxy polyetlryleneglycol (n=23) 1140 parts (1.1 moles), methacrylic acid 340 part:s (3.9 moles), p-benzoquinone 0.3 parts and concentrated sulfuric acici 7.2 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring but the reaction was discontinued because a large amount of insoluble gel came to be deposited about one hour the start.
Comparison Exaniple 6 (Production of polyetherester monomer (r-5)) Methoxy polyethyleneglycol (n=23) 1140 parts (1.1 moles), methacrylic acid 340 parts (3.9 inoles), phenothiazine 0.3 parts and concentrated sulfuric acici 7.2 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring but the reaction was discontinued because a large amount of insoluble gel came to be deposited about one hour the start Coniparison Example 7 Production of polyetherester monomer (T-1)) Methoxy polyethyleneglycol (n=9) 1060 parts (2.5 moles), methacrylic acid 430 parts (5 moles), p-benzoquinone 2.2 parts, concentrated sulfuric acici 3.5 parts and benzene as solvent 1000 parts were placed inside a reactor to start an esterification reaction by raising the temperature while stirring while removing ge.nerated water by distillation. After the esterification reaction, the excess portion of inethacrylic acid and the benzene used as solvent were removed by bubbling nitro~en to obtain a product. This product was analyzed and identified as polyetherester monomer (T-1) with hydroxyl value 1.3, carboxyl value 1.2, esterification reaction rate 99%.
Data on tlte production of these polyetherester monomers are summarized in Tables 1 and. 2.
Table 1 Examples R' A R' R' PE/ Inhibitor Acid Teinp. Pressure UA Catalyst ( C) (kPa) Test Examples 1 P-1 S-1 A-1 H S--1 1/2.0 I-1(0.21) C-1 (0.23) 125-130 12-2.5 2 P-2 S-1 A-2 H S-=1 1/3.5 I-1(0.18) C-1 (0.49) 125-130 10-:2.5 3 P-3 S-1 A-3 H S-1 1/3.6 I-1(0.15) C-1 (0.31) 125-130 7-1.5 4 P-4 S-2 A-4 H S--1 1/3.2 1-1(0.13) C-2 (0.68) 125-130 5-1.5 5 P-5 S-3 A-5 H S-=1 1/5.0 I-1(0.15) C-3 (0.80) 125-130 5-1.5 6 P-6 S-1 A-2 H S-=1 1/3.5 I-2(0.19) C-4 (0.47) 125-130 10-2.5 7 P-7 S-1 A-3 H S-1 1/4.1 I-3(0.16) C-5 (0.54) 125-130 5-1.5 Com E xamples 1 R-1 S-1 A-1 H S-1 1/2.0 1-1(1.0) C-1 (0.23) 125-130 12-2.5 2 r-1 S-1 A-1 H S-1 1/2.0 --- C-1 (0.23) *1 *1 3 r-2 S-1 A-1 H S-1 1/2.0 i-4(0.21) C-1 (0.23) *1 *1 4 r-3 S-1 A-1 H S-1 1/2.0 i-5(0.33) C-1 (0.23) *1 *1 5 r-4 S-1 A-2 H S-1 1/3.5 1-1(0.02) C-1 (0.49) *1 *1 6 r-5 S-1 A-2 H S-1 1/3.5 1-2(0.02) C-1 (0.49) *1 *1 7 T-1 S-1 A-1 H S-1 1/2.0 1-1(0.21) C-1 (0.23) In Table 1:
"Inhibitor" indicates "Polymerization inhibitor" and shows the kind and the weight % (in parentheses) used witli respect to polyalkyleneglycol with a.
closed end.
"Acid Catalyst" shows the kind and the weight % (in parentheses) used with respect to the total ainount of lkyleneglycol with a closed end and unsaturated carboxylic acid.
"PE/UA" indicates the niolar ratio of polyalkyleneglycol with a closed end shown by Formula 1 and unsaturated carboxylic acid shown by Formula 2.
*1 indicates that the reaction was discontinued.
S-1: Metllyl group S-2: Benzyl group S-3: Lauryl group A-1: Residual group obtained by renioving all hydroxyl groups from polyethyleneglycol with rf:petition number of oxyethylene groups equal to 9.
A-2: Residual group obtained by removing all hydroxyl groups from polyethyleneglycol with repetition number of oxyethylene groups equal to 23.
A-3: Residual groLip obtained by renloving all hydroxyl groups from polyethyleneglycol with repetition number of oxyethylene groups equal to 75.
A-4: Residual gro:ap obtained by i-emoving all hydroxyl groups from polyethyleneglycol with repetition number of oxyethylene groups equal to 90.
A-5: Residual group obtained by removing all hydroxyl groups from polyethyleneglycol with repetition nuinber of oxyethylene groups equal to 120.
I-1. p-benzoquinone I-2: phenothiazine 1-3: Mixture of p-benzoquinone/phenothiazine = 50/50 as weight ratio i-4: Hydroquinone i-5: Hydroquinone monomethyl ether C-1: 98% concentrated sulfuric acid C-2: Mixed acid witli 98% concentrated sulfuric acid and p-toluene sulfonic acid at weight ratio of 5/2.
C-3: Mixed acid wit1198% concentrated sulfuric acid and p-toluene sulfonic acid at weight ratio of 5.5/2.5.
C-4: Mixed acid with 98% concentrated sulfuric acid and p-toluene sulfonic acid at weight ratio of 4.5/2.5.
C-5: Mixed acid with 98% concentrated sulfuric acid and p-toluene sulfonic acid at weiglit ratio of 4/3.
Table 2 Examples Abnormal Generation Esterification Viscosity of Gel Reaction Ratio Iricrease (%) Test Examples Comparison Examples 2 r-1 B B *2 3 r-2 B B *2 4 r-3 B B *2 5 r-4 B B *2 6 r-5 B B *2 In Table 2:
For the evaluation of pc-esence/absence of abnormal viscosity increase:
A: No abnormal viscosity increase during esterification reaction B: Presence of abnormal viscosity increase during esterifrcation reaction For the evaluation of presence/absence of gel generation:
A: NID ;eneration of inscl,.,'-'e gel during esterification reaction B: Presence of generation of insoluble gel during esterification reaction *:': Esterification reaction ratio not measurable because esterification reaction was discontinued due to abnormal viscosity increase or generation of insoluble gel Part 2: Production of water_soluble vinyl copolxmers as cement dispersants Test Exam le 8 Pi-oduction ofwater-soluble vinyl copolymer (D-1)) Polyetlier ester monomer (P-1), obtained in Part 1, 152 parts (0.306 moles), metliacrylic acicl 56 parts (0.65 moles), 3-mercaptopropionic acid 2.1 part and water 330 parts were added to(yether and the atmosphere was replaced with nitrogen after they were dissolved uniformly by stirring. While the temperature of the reacting system was maintained at 80 C in the nitrogen environment by means of a warm bath, polymerization was started by dropping 20% aqueous solution of'sodiuin persulfate 8 parts. The polymerization reaction 5 was continued for 5 hours and an aqueous solution of water-soluble vinyl copolymer was obtained. This water-soluble vinyl copolymer was analyzed and identified as water-soluble vinyl copolymer (D-1) with average numerical molecular weight of 12500 having 3 5 molar % of component unit derived from polyetherester monomer (P-1) and 65 molar % of component unit derived from 10 methacrylic acid.
Test Example 9 (Production of water-soluble vinyl copolymer D-2'1) Polyetherester monomer (P-1), obtained in Part 1, 150 parts (0.30 moles), methacrylic acid 55 parts (0.64 moles), sodium methallylsulfonate 13 15 parts (0.082 moles), water 330 parts and aqueous solution of sodium hydroxide 80 parts were added together and the atmosphere was replaced with nitrogen after they were dissolved uniformly by stirring. While the temperature of the reacting system was mairrtained at 60 C in the nitrogen environment by means of a warm bath, polymerization was started by dropping 20% aqueous solutiori of 20 sodium persulfate 10 parts. T'he polymerization reaction was continued for hour-, ind 30% aqueous sollution of sodiuin hydroxide was added thereafter for a complete neutralization to obtain an aqueous solution of water-soluble vinyl copolyrner. This water-soluble vinyl copolymer was analyzed and identified as water-soluble vinyl copolymer (D-2) with average numerical molecular weight of 8800 havinix, 33 molar /o of'component unit derived from polyetherester rnonomer (P-1), 61 molar 'o of' component unit derived fr-om methacrylic acid and 6 molar % of component unit derived from sodium methallylsulfonate.
Test Examples 1 U_2l (Pr-oduction of water-soluble vinyl copolymers D-Water-soluble vinyl copolyrners (D-3)-(D-14) were produced as in Test Example 8 or 9. The details are shown in Table 3.
Table 3 Test Water- Ratio of Copolymerization Average Examples Soluble (molar %) Numerical Vinyl Molecular Copolymer a b c d Weight In Table 3:
a: Polyetherester rnonomer/molar %
b: Metliacrylic acid c: Sodium nlethacrylate d: Sodium methallyl sulfonate Cornparison Exam)le 8(Production of water-soluble vinyl copolymer Water-so~uble vinyl copolymer (DR-1) was produced as Comparison Example 8 in the same way as described in Test Example 8 for the production of %vater-soli.rble vinyl copolymer (D-1) except that "polyetherester monomer (P-1) 152 parts" was replaced by "polyetherester monomer (R-1)., obtained in Part 1, 152 parts".
Coinparison Exarri-Ae 9(Production of water-soluble vinyl copolymer ~DT-Water-soluble vinyl copolymer (DT-1) was produced as Comparison Example 9 in the same way as described in Test Example 8 for the production of water-soluble vinyl copolymer (D-1) except that "polyetherester monomer (P-1) 152 parts" was replaced by "polyetherester monomer (T-1), obtained in Part 1, 152 parts".
Coi-nparison Example 10 (Production of water-soluble vinyl copolymer (DT-2)) Water-soluble vinyl copolymer (DT-2) was produced as Comparison Example 8 in the same way as described in Test Example 9 for the production of water-soluble vinyl copolymer (D-2) except that "polyetherester monomer (P-1) 150 parts" was replaced by "polyetherester monomer (T-1), obtained in Part 1, 150 parts".
Part 3: Preparation and Evaluation of Concrete Preparation of Concrete Samples Concrete samples were prepared as follows under the conditions shown in T'able 4.
lormal portland cement (specific weight = 3.16; braine value =
3300), fine aggregates (Ooi-gawa River sand with specific weight = 2.63) and coarse aggregates (cn.istieci stones from Okazaki with specific weight = 2.63) were sequentially added into a pan-type forced kneading mixer with capacity 50 liters and subjected to a free kneading pi-ocess for 15 seconds. Next, the water-soluble vinyl copolymer s produced in Part 2 as cement dispersants were each added with water and kneaded at a rate of'O. 1-1.5 weight % with respect to the cement (as converted to solid component) such that the target slump would be within the range of 21 1 ci-n, aiid the mixture was kneaded for 2 minutes.
A,n agent for controlling the amount of air was also added in each case such that the target amount of air would. be 4.0-5.0%.
Coi-nparison Example 10 (Production of water-soluble vinyl copolymer (DT-2)) Water-soluble vinyl copolymer (DT-2) was produced as Comparison Example 8 in the same way as described in Test Example 9 for the production of water-soluble vinyl copolymer (D-2) except that "polyetherester monomer (P-1) 150 parts" was replaced by "polyetherester monomer (T-1), obtained in Part 1, 150 parts".
Part 3: Preparation and Evaluation of Concrete Preparation of Concrete Samples Concrete samples were prepared as follows under the conditions shown in T'able 4.
lormal portland cement (specific weight = 3.16; braine value =
3300), fine aggregates (Ooi-gawa River sand with specific weight = 2.63) and coarse aggregates (cn.istieci stones from Okazaki with specific weight = 2.63) were sequentially added into a pan-type forced kneading mixer with capacity 50 liters and subjected to a free kneading pi-ocess for 15 seconds. Next, the water-soluble vinyl copolymer s produced in Part 2 as cement dispersants were each added with water and kneaded at a rate of'O. 1-1.5 weight % with respect to the cement (as converted to solid component) such that the target slump would be within the range of 21 1 ci-n, aiid the mixture was kneaded for 2 minutes.
A,n agent for controlling the amount of air was also added in each case such that the target amount of air would. be 4.0-5.0%.
Table 4 Water/ Ratio of fine Unit amount (kg/m3) cement aggregates ratio (%) (%) Water Cement Fine Coarse aggregates aggregates Evaluation of Concrete Samples Slump of each concrete sample prepared was evaluated as follows, both immediately after tl-ie kneading (t=0) and after it was left quietly for minutes (t==60) according to JIS-A1 101 (Japanese Industrial Standard). Ttie results of evaluation are shown in Table 5.
Slump loss: ((Slump at t=60)/(Slump at t=0))x100 Ainount of air: Measured according to JIS-Al 128 Compressive Strength (CS): Measured according to JIS-A1108.
Table 5 No. Cement Dispersanl t=0 t=60 Slulnp CS (N/mmZ) Loss Type Alnount Slulnp Air SlLltnp Air (~~o) 7 days 28 days (part) (cm) (%) (cln) (%) 1 D-1 0.22 21,7 4.5 18.0 4.3 82.9 34.0 45.2 2 D-2 0.24 21.3 4.5 20.0 4.4 93.9 34.2 45.5 3 D-3 0.21 21J 4.3 18.3 4.3 85.1 34.1 45.0 4 D-4 0 22 21.8 4.2 19.9 4.2 91.3 34.5 45.3 5 D-5 0 20 21.3 4.4 18.1 4.0 85.0 35.0 46.3 6 D-6 0.21 21.1 4.5 18.8 4.4 89.1 34.7 45.2 7 D-7 0 23 21.6 4.6 18.5 4.5 85.6 34.4 45.5 8 D-8 0 21 21.8 4.5 19.7 4.2 90.4 34.2 45.3 9 D-9 026 21.-4 4.4 19.5 4.3 91.1 34.6 45.6 10 D-10 0 28 21.2 4.7 20.0 4.6 94.3 34.0 45.1 11 D-11 0 22 2 1.7 4.6 18.9 4.2 87.1 34.8 46.0 12 D-12 0,23 21.3 4.5 20_ l 4.1 94.3 35.0 46.2 13 D-13 021 21.5 4.3 15.2 4.2 84.7 34.6 45.7 14 D-14 0 23 21.6 4.6 19.5 4.-1 90_3 34.3 45.1 15 DR-I 0.-13 21.2 4.5 13.7 4.2 64.6 31.2 40.9 16 DT-1 0.22 21`5 4.5 17.8 4.1 82.8 34.0 45.0 17 DT-2 0.24 21.2 4.5 19.8 4.4 93.4 34.1 45.5 In Table 5:
"7 clays" and "28 days": Age of tested product Amount of added cement dispersant is shown as that of water-soluble vinyl copolymer in solid f'orm with i-espect to 100 parts of cement.
As can be understood from the above, the present invention makes it possible to produce polyetherester monomers of a high quality in the absence of any solvent and to provide cement dispersants with improved properties comprising water-soluble vinyl copolymers which can be produced from such polyetherester monomers are an intermediate product.
Slump loss: ((Slump at t=60)/(Slump at t=0))x100 Ainount of air: Measured according to JIS-Al 128 Compressive Strength (CS): Measured according to JIS-A1108.
Table 5 No. Cement Dispersanl t=0 t=60 Slulnp CS (N/mmZ) Loss Type Alnount Slulnp Air SlLltnp Air (~~o) 7 days 28 days (part) (cm) (%) (cln) (%) 1 D-1 0.22 21,7 4.5 18.0 4.3 82.9 34.0 45.2 2 D-2 0.24 21.3 4.5 20.0 4.4 93.9 34.2 45.5 3 D-3 0.21 21J 4.3 18.3 4.3 85.1 34.1 45.0 4 D-4 0 22 21.8 4.2 19.9 4.2 91.3 34.5 45.3 5 D-5 0 20 21.3 4.4 18.1 4.0 85.0 35.0 46.3 6 D-6 0.21 21.1 4.5 18.8 4.4 89.1 34.7 45.2 7 D-7 0 23 21.6 4.6 18.5 4.5 85.6 34.4 45.5 8 D-8 0 21 21.8 4.5 19.7 4.2 90.4 34.2 45.3 9 D-9 026 21.-4 4.4 19.5 4.3 91.1 34.6 45.6 10 D-10 0 28 21.2 4.7 20.0 4.6 94.3 34.0 45.1 11 D-11 0 22 2 1.7 4.6 18.9 4.2 87.1 34.8 46.0 12 D-12 0,23 21.3 4.5 20_ l 4.1 94.3 35.0 46.2 13 D-13 021 21.5 4.3 15.2 4.2 84.7 34.6 45.7 14 D-14 0 23 21.6 4.6 19.5 4.-1 90_3 34.3 45.1 15 DR-I 0.-13 21.2 4.5 13.7 4.2 64.6 31.2 40.9 16 DT-1 0.22 21`5 4.5 17.8 4.1 82.8 34.0 45.0 17 DT-2 0.24 21.2 4.5 19.8 4.4 93.4 34.1 45.5 In Table 5:
"7 clays" and "28 days": Age of tested product Amount of added cement dispersant is shown as that of water-soluble vinyl copolymer in solid f'orm with i-espect to 100 parts of cement.
As can be understood from the above, the present invention makes it possible to produce polyetherester monomers of a high quality in the absence of any solvent and to provide cement dispersants with improved properties comprising water-soluble vinyl copolymers which can be produced from such polyetherester monomers are an intermediate product.
Claims (13)
1. A method of producing a water-soluble vinyl copolymer for cement dispersant, comprising:
a first step of producing a polyetherester monomer shown by Formula 3 by causing an esterification reaction of a polyalkyleneglycol with a closed end shown by Formula 1 and an unsaturated carboxylic acid shown by Formula 2 by using an acid catalyst under a heated and reduced-pressure condition in the absence of a solvent and in the presence of one selected from the group consisting of p-benzoquinone, phenothiazine and a mixture thereof in an amount of 0.03-0.5 weight % of the polyalkyleneglycol with a closed end while distilling away generated water:
R3-O-A-OH (Formula 1) where R1 and R2 are each H or methyl group, R3 is selected from the group consisting of an alkyl group with 1-22 carbon atoms, a benzyl group, a phenyl group and an alkylphenyl group having an alkyl group with 1-12 carbon atoms, and A is residual group obtained by removing all hydroxyl groups from a polyalkyleneglycol with a repetition number of oxyalkylene units 5-250, the oxyalkylene units consisting either only of oxyethylene units or of both oxyethylene units and oxypropylene units; and a second step of obtaining the water-soluble vinyl copolymer by a radical copolymerization of the polyetherester monomer obtained in the first step and a vinyl monomer in an aqueous solution, the vinyl monomer being copolymerizable with the polyetherester monomer.
a first step of producing a polyetherester monomer shown by Formula 3 by causing an esterification reaction of a polyalkyleneglycol with a closed end shown by Formula 1 and an unsaturated carboxylic acid shown by Formula 2 by using an acid catalyst under a heated and reduced-pressure condition in the absence of a solvent and in the presence of one selected from the group consisting of p-benzoquinone, phenothiazine and a mixture thereof in an amount of 0.03-0.5 weight % of the polyalkyleneglycol with a closed end while distilling away generated water:
R3-O-A-OH (Formula 1) where R1 and R2 are each H or methyl group, R3 is selected from the group consisting of an alkyl group with 1-22 carbon atoms, a benzyl group, a phenyl group and an alkylphenyl group having an alkyl group with 1-12 carbon atoms, and A is residual group obtained by removing all hydroxyl groups from a polyalkyleneglycol with a repetition number of oxyalkylene units 5-250, the oxyalkylene units consisting either only of oxyethylene units or of both oxyethylene units and oxypropylene units; and a second step of obtaining the water-soluble vinyl copolymer by a radical copolymerization of the polyetherester monomer obtained in the first step and a vinyl monomer in an aqueous solution, the vinyl monomer being copolymerizable with the polyetherester monomer.
2. The method of claim 1 wherein the polyalkyleneglycol and the unsaturated carboxylic acid are used at a molar ratio of 1/1.5-1/7 and an excess amount of the unsaturated carboxylic acid is removed by distillation after the esterification reaction in the first step.
3. The method of claim 2 wherein p-benzoquinone is present in an amount of 0.1-0.25 weight % based of the polyalkyleneglycol in the first step.
4. The method of claim 2 wherein the esterification reaction in the first step is carried out while the temperature of the polyalkyleneglycol and the unsaturated carboxylic acid is increased gradually or in a stepwise manner within 105-135°C and the pressure thereof is reduced gradually or in a stepwise manner within 15-0.5kPa.
5. The method of claim 3 wherein the esterification reaction in the first step is carried out while the temperature of the polyalkyleneglycol and the unsaturated carboxylic acid is increased gradually or in a stepwise manner within 105-135°C and the pressure thereof is reduced gradually or in a stepwise manner within 15-0.5kPa.
6. The method of claim 4 wherein the acid catalyst is added in the first step in an amount of 0.2-1.5 weight % based on the total amount of the polyalkyleneglycol and the unsaturated carboxylic acid.
7. The method of claim 5 wherein the acid catalyst is added in the first step in an amount of 0.2-1.5 weight % based on the total amount of the polyalkyleneglycol and the unsaturated carboxylic acid.
8. The method of claim 6 wherein the repetition number of the oxyalkylene units in A is 5-250, and the oxyalkylene units consist only of oxyethylene units.
9. The method of claim 7 wherein the repetition number of the oxyalkylene units is 5-250, and the oxyalkylene units consist only of oxyethylene units.
10. The method of claim 8 wherein (meth)acrylic acid and/or salt thereof is used as the vinyl monomer in the second step.
11. The method of claim 9 wherein (meth)acrylic acid and/or salt thereof is used as the vinyl monomer in the second step.
12. The method of claim 8 wherein (meth)acrylic acid and/or salt thereof and methallyl sulfonate are used as the vinyl monomer in the second step.
13. The method of claim 9 wherein (meth)acrylic acid and/or salt thereof and methallyl sulfonate are used as the vinyl monomer in the second step.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-287542 | 1999-10-08 | ||
| JP28754299 | 1999-10-08 | ||
| JP2000226606A JP3327901B2 (en) | 1999-10-08 | 2000-07-27 | Method for producing polyetherester monomer |
| JP2000-226606 | 2000-07-27 | ||
| US09/660,699 US6444780B1 (en) | 1999-10-08 | 2000-09-13 | Method of producing polyetherester monomer and cement dispersants |
| US09/660,699 | 2000-09-13 |
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