JPS62285924A - Alkoxytitanium surface-treating agent - Google Patents

Abstract

PURPOSE:To obtain the title surface-treating agent excellent in the effect of reducing the viscosity of a complex system of a highly polar polymer medium and a filler, containing a reaction product of a tetraalkoxytitanium (condensate of hydrolysate) with phthalic anhydride or a phthalic half ester. CONSTITUTION:An alkoxytitanium (a) (e.g., tetraisopropoxytitanium) and/or an alkoxytitanium polymer (b) (average degree of condensation <=6) obtained by hydrolysis and condensation of component (a) is reacted with phthalic anhydride (c) or a phthalic half ester (d) at 40-80 deg.C for 2-6hr to obtain a free substituent-containing alkoxytitanium derivative comprising 30-90% groups of formula I (wherein R is a linear or branched 1-6C alkyl) and groups of formula II (wherein R' is R). This derivative is dissolved, if necessary, in a solvent to obtain an alkoxytitanium surface-treating agent.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an alkoxytitanium-based surface treatment agent, and more specifically, to an alkoxytitanium-based surface treatment agent, and more particularly, to an alkoxytitanium-based surface treatment agent. The present invention relates to a surface treatment agent containing as an active ingredient a titanium alkoxide derivative in which part of the moiety is substituted with a phthalic acid halfester residue.

The surface treatment agent of the present invention improves the dispersibility and processability of the filler in the polymer when producing a composite of a solid substance and a polymer, for example, a composite in which a filler is dispersed in the polymer. In order to improve the physical properties of the resulting composite, the surface of the filler is treated or the filler is used by being added and mixed with a polymeric medium.

[Conventional technology]

It has been well known that when producing a composite of a solid material and a polymeric material, the properties of the composite can be improved by surface treating the solid material using an organic titanium compound. For example, by using a fatty acid ester of alkoxy titanium as a surface treatment agent for a composite system of kaolin as a filler and a polymer material such as polypropylene, polyethylene, or ethylene propylene rubber, the polymer material of the filler can be It is disclosed in Japanese Patent Publication No. 49-39196 that the dispersibility, processability, and various physical properties of the cured product are improved. Furthermore, it has been reported in JP-A-56-84723 that a fatty acid ester of alkoxy titanium similar to the above is effective as a surface treatment agent for composite systems such as calcium carbonate and epoxy resin, silica and liquid polysulfide rubber, and calcium carbonate and polyethylene. It is disclosed in the publication No.

On the other hand, regarding the surface treatment agent containing as an active ingredient an alkoxytitanium derivative in which phthalic acid halfester residues are introduced into some of the free substituents of alkoxytitanium and/or its hydrolyzed condensation product according to the present invention, No known literature is available.

(Problems to be Solved by the Invention) The fatty acid esters of alkoxy titanium disclosed in the above-mentioned references are found in a composite system of a wide variety of fillers and polymeric substances (resins). Although an excellent effect is observed in combination with oleic acid, there are cases where no effect is shown by changing the combination. Alkoxytitanium fatty acid ester is extremely effective as a surface treatment agent for composite systems of kaolin and polyethylene or polypropylene, but it is also effective as a surface treatment agent for composite systems of kaolin and polyvinyl chloride, composite systems of calcium carbonate and polyamide, etc. Even when used, almost no treatment effect is observed.In addition, alkoxytitanium fatty acid ester synthesized from 1 mol of tetraisopropoxytitanium and 3.19 mol of isostearic acid is treated with barium sulfate and high-density polyethylene (H
When used as a surface treatment agent for a composite system with DPE), the melt index, tensile strength, impact strength, etc. are improved, but when used as a surface treatment agent for a composite system with other composite systems, such as kaolin-polyvinyl chloride system, talc-polyurethane system, Even when used for silica-epochine resin systems, calcium carbonate-unsaturated polyester systems, etc., almost no surface treatment effect is observed.

As mentioned above, the well-known alkoxy titanium fatty acid esters are effective only in specific composite systems, and can be applied to a wider range of composite systems, especially highly polar polymer systems, such as polyvinyl chloride and polyimide. , epoxy resin, etc., the surface treatment effect is hardly recognized.

The present invention aims to provide a surface treatment agent that has excellent effects on filler dispersibility, processability, physical properties of cured products, etc. even in composite systems of fillers and highly polar polymeric substances. purpose.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have discovered that an alkoxytitanium derivative synthesized from tetraalkoxytitanium and phthalic acid hafester can be used as a surface treatment agent for a composite system of fillers and polymeric substances. It was discovered that it exhibits excellent effects as an active ingredient, and the present invention was completed.

The present invention relates to a reaction product of tetraalkoxytitanium and/or a hydrolyzed condensation product (polymer) of tetraalkoxytitanium having an average degree of condensation of 6 or less and phthalic anhydride or phthalic acid halfester, wherein 35 ~
90% is Ro- group (herein, R represents an alkyl group having 1 to 6 carbon atoms having a straight chain or a side chain) and the remainder is -
ooc-c.

It is characterized by containing an alkoxytitanium derivative which is a H, -COOR' group (here, Ro represents an alkyl group having 1 to 6 carbon atoms having a straight chain or side chain that is the same as or different from R). It is a surface treatment agent.

The surface treatment agent of the present invention has the following general formula (1): % formula % (where R and Ro represent the same meanings as above, and n
is 1 or 2. ,) has a -Ti0-Ti- bond in one molecule, and contains 35 to 90% of RO- groups and the remainder is 00CCJ=-COORo
The active ingredient is an alkoxytitanium derivative/polymer having a group as a free substituent and having an average degree of condensation of 6 or less, or a mixture of these monomers and a polymer.

R and R'' in the substituents include a methyl group, ethyl 5, n-propyl group, i-propyl group, n-butyl group,
Examples include alkyl groups having 1 to 6 carbon atoms having a straight chain or a side chain such as a tert-butyl group, a pentyl group, and an n-hexyl group, and these may all be the same substituent or different substituents. The surface treatment agent of the present invention may contain phthalic anhydride per mole of tetraalkoxytitanium represented by the general formula: (RO)*Ti (herein, R represents the same meaning as above). Alternatively, it can be synthesized by reacting 1 to 2 moles of phthalic acid halfester.

The reaction between tetraalkoxytitanium and phthalic anhydride is represented by the following reaction formula (3), and the reaction between tetraalkoxytitanium and phthalic acid halfester is represented by the following reaction formula (4).

(RO)*Ti + ncJLcz(h −→(RO)
+n-, 1. Ti(OOC-CJ4-GOOR), l
...(3) (RO)4Ti + nHOOc-
CJa C0OR' -→(RO)+4-1++Ti
(OOCc, H,, C0OR'), l+ROH・-(4
) (Here, R and R' represent the same meanings as above,
n is 1 or 2. ) In addition, in these reactions, dialkyl esterification of phthalic anhydride or phthalic acid hafester occurs as a side reaction, and as a result of this dialkyl esterification reaction, alkoxytitanium undergoes condensation polymerization, and some of the alkoxytitanium derivatives/polymers are By-product. Therefore, in these reactions, a mixture of the alkoxytitanium derivative/monomer obtained by reaction formula (3) or (4) and a conductor/polymer in the molecule is obtained under normal reaction conditions, and in particular, by-products are not eliminated. It can be used as a surface treatment agent without separation. Alternatively, the monomer and polymer may be separated by extraction or the like, and each may be used as a surface treatment agent.

In addition, the molar ratio of the tetraalkoxytitanium to the total number of free substituents of the alkoxytitanium polymer having an average degree of condensation of 6 or less that has been previously hydrolyzed and polycondensed is 0.1.
~0.65% of the free fiRo groups of the alkoxytitanium polymer are substituted with phthalic acid hafester residues by reacting with phthalic anhydride or phthalic acid hafester having an average degree of condensation of 6 or less. Surface treatment agents containing alkoxy titanium derivatives/polymers as main components can be produced.

In these reactions, as the starting material tetraalkoxytitanium, tetraisopropoxytitanium and tetra-n-butoxytitanium are preferably used from the viewpoint of hydrolyzability of the surface treatment agent, ease of availability, and the like. On the other hand, phthalic acid hafester can be synthesized by equimolar reaction of phthalic anhydride and alcohol, and in the reaction,
There is no particular need to use pure phthalic acid halfester, and the reaction solution obtained in this reaction may be used as it is. Further, as the phthalic acid hafester, a hafester with isopropanol or normal butanol is preferably used.

The reaction of the tetraalkoxytitanium monomer and/or tetraalkoxytitanium polymer with phthalic anhydride or phthalic acid halfester is carried out under stirring at a temperature of 40 to 80° C. for 2 to 6 hours in the presence or absence of a solvent. The hafestation reaction of phthalic anhydride is carried out by stirring and maintaining at a temperature of 40 to 80° C. for 2 to 6 hours in the presence or absence of a solvent.

The surface treatment agent of the present invention can be blended into a wide range of mixed systems of polymeric media and fillers, and used to reduce the viscosity of the mixed system, improve the dispersibility of fillers, and improve the physical properties of cured products. be done. These may be used alone or dissolved in a solvent, and may also be used in combination with other surface treating agents or solvents.

Examples of polymeric media include polyethylene, polypropylene, polyvinyl chloride, polyester, polycarbonate, alkyd resin, acrylic resin, polyvinylidene fluoride, polyamide, polysulfone, polysulfide, polyphenylene oxide, xylene resin, nitrocellulose, chlorinated rubber, chlorinated Examples include polyethylene, polystyrene, styrene-butadiene copolymer, polyacrylonitrile, and the like. On the other hand, as fillers, relatively inert solids are added to polymeric materials for the purpose of reducing the unit cost of the polymeric material, improving processability and physical properties, imparting color effects, etc. For example, calcium carbonate, kaolin, clay, mica, talc, calcium silicate, titanium oxide, iron oxide, silica, carbon blank,
Examples include calcium sulfate, barium sulfate, aluminum powder, zinc powder, glass fibers, wood flour, paper and fiber powders, synthetic and natural powders, pigments and extender pigments used in the paint industry, and the like.

The surface treatment agent of the present invention can be added to and mixed with the polymer medium in advance, added at the same time as the filler is mixed into the polymer medium, or coated on the surface of the filler in advance. The amount of the surface treatment agent that may be used in the above method is 0.1 to 5 parts by weight, preferably 0.2 to 1 part by weight, per 100 parts by weight of the filler.

If the amount used is too small, the effect of use will be small, and even if it is used in excess, the expected increase in the effect of use will not be observed.

[For production]

The surface treatment agent of the present invention is characterized in that, as described above, the active ingredient is an alkoxytitanium derivative having a relatively short-chain alkoxy group and a phthalic acid hafester residue as a free substituent. The alkoxy group (IIO- group) is a hydrolyzable reactive group, R is preferably an alkyl group having 1 to 6 carbon atoms, and I? If the carbon number of phthalic acid hafester residue (-00
CC, 11, coOR'' group) is different from titanium alkoxide derivatives which have a substituent consisting only of a benzene ring, such as benzoic acid residue (00CC6H5 group), in its structure. It is preferable that Ro is an alkyl group having 1 to 6 carbon atoms, and a large number of carbon atoms in R'' is not preferable because it causes selectivity to the resin that is the polymeric medium. More preferably, Ro has 3 or 4 carbon atoms. In addition, the average degree of condensation of the alkoxy titanium derivative is preferably 6 or less. If the average degree of condensation is too large, the molecules as a surface treatment agent will become too large, making it difficult to effectively adhere to the surface of the filler. Treatment effectiveness decreases. Furthermore, the content of alkoxy groups in the free substituents of the alkoxy titanium derivative is preferably 35 to 90%; if the alkoxy group content is too low, the reactivity with the filler will decrease, or if the content is too high, In this case, the amount of phthalic acid halfester residues becomes too small and the appearance of lipophilicity decreases.

The surface treatment agent of the present invention has a well-balanced polarity and non-scratch property as a whole structure by specifying the structure of the alkoxy titanium derivative as its active ingredient as described above. As a result, when a filled polymer system, which is a mixed system of a polymer medium and a filler, is used in paints, inks, composite resins, etc., the viscosity-reducing effect, dispersion effect, physical property improvement effect, etc. Unlike titanium-based surface treatment agents, it is presumed that this phenomenon occurs even in polymer matrices with various polarities. In particular, excellent surface treatment effects are achieved even in composite systems of highly polar polymers, such as polyvinyl chloride, polyamides, unsaturated polyesters, epoxy resins, etc., and fillers.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the scope of the present invention is not limited in any way by the following examples.

Note that "parts" and "%" in the following examples are based on weight unless otherwise specified.

(1) Synthesis of alkoxy titanium derivatives tal samples (T-1) (T-2) and comparative samples (
CT-1) Into a reaction flask equipped with a stirrer, a thermometer, an air-cooled condenser, and a heating device, 1 mol (284 parts) of tetraisopropoxytitanium was charged, and 1 mol (284 parts) of tetraisopropoxytitanium was added to the flask, and 1 mol (284 parts) of tetraisopropoxytitanium
mol (148 parts) was added slowly.

Then, the mixture was heated to 65°C and kept stirring for 3 hours to obtain 432 parts of a viscous liquid (T-1) that was pale yellow and transparent and had a viscosity of 150 voids at 25°C.

As a result of analyzing the obtained (T-1) by infrared absorption spectrum (IR), absorption based on benzene rings and ester bonds was observed, and as a result of quantitative analysis using the ignition residue (Tt(h) method), The Ti content was 11.1%.

From the above analysis results, it can be concluded that (T-1) is mainly composed of an alkoxytitanium derivative in which one of the isopropoxy groups of tetraisopropoxytitanium is replaced with a phthalic acid monoisopropyl ester residue. estimated.

In addition, in the synthesis of (T-1), 1 mol (284 parts) of tetraisopropoxytitanium was replaced with 1 mol (340 parts) of tetra-n-butoxytitanium, and the amount of phthalic anhydride used was replaced with 2 mol (296 parts). Other than that, the reaction was carried out under the same conditions as for the synthesis of (T-1), with a Ti content of 7.55% and a
A product (T-2) was obtained in which the main component was an alkoxytitanium derivative monomer in which two of the butquin groups of tetra-n-butoxytitanium were substituted with phthalic acid mono-n-butyl ester residues and had a viscosity of 320 voids at 5°C.

Furthermore, in the synthesis of (T-1), 1 mol (122 parts) of benzoic acid was used instead of phthalic anhydride, and the reaction temperature was changed to 70%.
The reaction was carried out under the same conditions as above except that the temperature was changed to
A comparative sample (CT-1) was obtained, the main component of which was a monomer of an alkoxy titanium derivative in which one of the isopropoxy groups of tetraisopropoxy titanium was substituted with a benzoic acid residue and had a viscosity of 175 voids at 25°C.

These specifications are shown in Table 1.

Mountain) Sample (T-3), comparative sample (CT-2), and the same reaction apparatus as that used for the synthesis of sample (T-1).
Prepare 1 mol (396 parts) of tetrapentoxytitanium,
Equimolar reaction product of phthalic anhydride and n-butanol 222
(equivalent to 1 mol as phthalic acid mono-n-butyl ester) was gradually added and heated to 70°C, and at that temperature
After stirring and holding for an hour, it becomes pale yellow and transparent with a viscosity of 3 at 25°C.
613 parts of a viscous liquid (T-3) with 90 voids was obtained.

As a result of IR analysis of the obtained (↑-3), absorption based on benzene rings and ester bonds was observed, and as a result of quantitative analysis using the ignition residue (Tiet) method, the Ti content was 7.77%. Met.

From the above analysis results, it is estimated that (T-3) is mainly composed of an alkoxytitanium derivative monomer in which one of the pentoxy groups of tetrapentoxytitanium is substituted with a phthalic acid mono-n-butyl ester residue. .

In the synthesis of (T-3), 1 mol (284 parts) of tetraisopropoxytitanium was used instead of tetrapentoxytitanium.
and 334 parts of an equimolar reaction product of phthalic anhydride and lauryl alcohol (equivalent to 1 mole as phthalic acid monolauryl ester) was used instead of the equimolar reaction product of phthalic anhydride and n-butanol. The reaction was carried out under the same reaction conditions as for the synthesis of T-3), and the viscosity at 25°C was 2.
A comparative sample (CT-2) was obtained, in which one of the isopropoxy groups of 25 poise tetraisopropoxytitanium was substituted with a monolauryl phthalate residue.

These specifications are shown in Table 1.

(C1 sample (T-4) 830 parts (1 mol) of a hydrolyzed condensation polymer (polymer) of tetraisopropoxy titanium having an average degree of condensation of 4 was added to the same reaction apparatus as that used for the synthesis of sample (T-1). equivalent) and prepare equimolar reaction product 4 of phthalic anhydride and n-butanol.
RO part (5 as phthalic acid mono-n-butyl ester)
(mol equivalent) was gradually added and heated to 70°C, stirred and held at that temperature for 3 hours, resulting in a pale yellow and transparent viscosity at 25°C: 56 G Q Whis (7) Viscosity? , it-like Th(T
-4) 1940 copies were obtained.

As a result of IR analysis of the obtained (T-4), absorption based on the benzene ring and ester bond was observed, and as a result of quantitative analysis using the ignition residue (TiO□) method, the Ti content was 9.90%. %Met.

From the above analysis results, (T-4) is mainly composed of an alkoxytitanium derivative polymer in which some of the free substituents of the isopropoxytitanium polymer are substituted with phthalic acid mono-n-butyl ester residues. estimated.

(T-4) specifications are shown in Table 1.

ldl Comparative sample (CT-3) Using the same reactor as that used for the synthesis of sample (T-1), 1 mol (284 parts) of tetraisopropoxy titanium and 3.1 mol (880 parts) of isostearic acid were used. 978 parts of a pale yellow transparent liquid (CT-3) having a viscosity of 1.25 voids at 25 DEG C. was obtained.

(CT-3) specifications are shown in Table 1.

(Space below) (2) Dioctyl phthalate - 200 parts of calcium carbonate-based dioctyl phthalate were added with the alkoxy titanium derivatives (T-1) to (T-4) and (CT-1) to (CT) synthesized in the above (1). -3) Dissolve 3 parts each of
Furthermore, 300 parts of calcium carbonate (manufactured by Shiraishi Kogyo ■, trade name: Whiten 5SB) was added, and 2 parts were added using a ball mill.
The mixture was kneaded for 0 hours.

The viscosity of the obtained kneaded product at 25°C was measured using a rotational viscometer (
Measurements were made using a Tokyo Keiki Co., Ltd.).

In addition, for comparison, the viscosity of a sample without the addition of an alkoxytitanium derivative was also measured.

The results of the viscosity measurements are shown in Table 2.

Table 2 (3) The alkoxytitanium derivatives (T-1) to (T-4) synthesized in the fi1 section above and (CT-1) ~ (CT
-3) were dissolved, and 80 parts of calcium carbonate (manufactured by Shiraishi Kogyo ■, trade name: Whiten 5SB) was added and kneaded for 20 hours using a ball mill. In addition, polyvinyl chloride (manufactured by Nippon Zeon, product name: Geon)
121) 100 parts of tribasic lead sulfate, 0.5 part of dibasic lead stearate and 2 parts of calcium stearate were added and mixed, and then kneaded using two rolls heated to 175 to 180°C.

The obtained kneaded product was preheated at 480° C. for 10 minutes and pressure molded at 30 g/cnl×180° C. for 5 minutes to obtain test pieces for measuring physical properties.

Using the obtained test piece, the tensile strength and elongation rate were measured according to JIs-6723, and the tensile strength and elongation rate were measured according to JrS-7210.
The melt index (M+>) was measured under the conditions of 190°C x 4,350g according to the following.

For comparison, a system without the addition of an alkoxytitanium derivative was also subjected to the same treatment and its physical properties were measured.

The measurement results are shown in Table 3.

(Leaving space below) Table 3 (4) Urethane-talc polyether polyol with average molecular weight 3000,0HV38.8 (Mitsui Tsuretan ■Product name: Diol 3
000) In 125 parts, alkoxy titanium derivatives (T-1) to (T-4) and (C
1 part each of T-1) to (CT-3) was dissolved, and 100 parts of talc (manufactured by Nippon Kurkuu, trade name: Simbon) was added and kneaded for 20 hours using a ball mill to form a polyether composition. Prepared.

The viscosity of the obtained polyether composition at 25° C. was measured using a rotational viscometer (manufactured by Tokyo Keikiken) and is shown in Table 4.

Next, N G O 3.0%, viscosity 7000CP (2
A base material was prepared by mixing 100 parts of a room-temperature curing elastomer (manufactured by Mitsui Urethane Co., Ltd., trade name: Yumi 1i-Prene P-305) and 60 parts of talc (manufactured by Nippon Talc ■, trade name: Simbon). Further, 1.5 parts of dibutyltin dilaurate was added to and mixed with the polyether composition prepared above to prepare a curing agent for the room temperature curing elastomer.

After mixing and defoaming 100 parts each of the above-prepared base agent and curing agent, the mixture was spread and applied in a sheet form on a Teflon plate, and left at room temperature for 14 days to cure.

Regarding the obtained cured product, a dumbbell type 3 test piece was prepared according to JIS K-6301, and the tensile strength and tear strength were measured according to JIS. These measurement results are shown in Table 4 together with a comparative example in which no alkoxytitanium derivative was added.

(Left below) (5) Polyamide resin - Calcium carbonate system - Calcium carbonate (manufactured by Shiraishi Kogyobu, product name: Whiten 5SB) 1
00 parts of the alkoxytitanium derivatives (T-1) to (T-4) and (CT-1) to (T-4) synthesized in section (1) above.
Surface treatment was performed with one part each of CT-3).

Polyamide pellets (Allied Chemica)
After kneading 100 parts of nylon 6) and 50 parts of the surface-treated calcium carbonate at 100°C using a kneader,
Cooled and ground.

Table 5 shows the melt index of the obtained pulverized product measured in accordance with JIS K-6760 at 190°C and 2.16 kg/c4.

Next, this pulverized material was put into an injection molding machine (manufactured by Nisshin Jushi Kogyo Co., Ltd.).
FS-75 model). The obtained molded product was exposed to water for 48 hours at a temperature of 20°C and a relative humidity of 45%,
Each physical property was measured in accordance with JIS K-6911. The measurement results are shown in Table 5 together with a comparative example using calcium carbonate not treated with an alkoxytitanium derivative.

Table 5 (6) Epoxy resin-calcium carbonate system Alkoxy titanium derivatives (T-1) to (T-4) prepared in item (5) above
) and 100 parts of calcium carbonate surface-treated with (CT-1) to (6-3) and 200 parts of bisphenol A diglycidyl ether with an average molecular weight of 380,
The mixture was kneaded using an Ishikawa Laikai machine. The viscosity of the kneaded product at 25°C measured using a rotational viscometer (manufactured by Tokyo Keiki ■, model B8R, rotor No. 7) is shown in Table 6 along with a comparative example using calcium carbonate untreated with an alkoxytitanium derivative. Shown below. To 100 parts of the obtained kneaded material, 80 parts of tetrahydrophthalic anhydride as a curing agent and 1 part of tris(dimethylaminomethyl)phenol as a curing accelerator were added and mixed, and after defoaming, the mixture was heated at 100°C for 2 hours and at 160'cx2. It was heated and cured for a certain amount of time.

Table 6 shows the physical properties of the obtained cured product measured according to JIS K-6911.

Table 6 The impact strength in the table represents the Izot impact strength.

〔Effect of the invention〕

As shown in the examples above, the surface treatment agent of the present invention has a viscosity-reducing effect in many polymeric media, especially in composite systems of highly polar polymeric media and fillers, and also It has an excellent effect on improving physical properties. Therefore, the range of application of the surface treatment agent of the present invention is wide, and in particular, the conditions for selecting a polymer system and a filler system are relaxed, making it possible to manufacture many polymer-filler composite systems.

The present invention provides a surface treatment agent that can be used in many polymer-filler composite systems, and has great industrial significance.

Claims (1)

[Claims] (1) A reaction product of tetraalkoxytitanium and/or a hydrolyzed condensation product (polymer) of tetraalkoxytitanium having an average degree of condensation of 6 or less and phthalic anhydride or phthalic acid half ester, which has 35 free substituents. ~90
% is RO- group (herein, R represents an alkyl group having 1 to 6 carbon atoms having a straight chain or a side chain) and the remainder is -OO
C-C_6H_4-COOR' group (here, R' has 1 to 1 carbon atoms and has a straight chain or side chain that is the same as or different from R)
6 represents an alkyl group. ) A surface treatment agent characterized by containing an alkoxytitanium derivative