JPH0321564B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION It is known in the art to reinforce resins with glass fibers. For example, the following patents disclose reinforcing resin materials with glass fibers using polyester resins and organosilicon compounds as adhesion promoters: (1) U.S. Pat. It discloses reinforcing elastomeric materials with glass fibers by a process consisting of impregnating the glass fiber bundle with an elastomer or resin polymer and then coating the glass fiber bundle with a material that is compatible with the elastomer. This patent discloses polyester resins as useful impregnation materials and organosilicon compounds as materials compatible with the elastomer. (2) US Pat. No. 2,931,739 discloses reinforcing resin materials with glass fibers using organosilicon compounds in combination with polyester resins as adhesion promoters. Although saturated polyesters are disclosed as preferred embodiments in this patent, unsaturated polyester resins are mentioned (see column 4 of this patent, lines 74-75;
Column lines 1-16; and Example 8). (3) US Pat. No. 3,252,825 discloses a method of coating glass fibers with a hydrolyzate of a condensation product of an aminosilane and a polymer or polymer product. This patent specifically mentions reacting an unsaturated polyester with alpha-aminopropyltriethoxysilane to form an aqueous sizing agent (see Example 4, column 6 of this patent). . (4) US Pat. No. 3,658,571 discloses a method for reinforcing elastomeric materials with glass fibers using compositions that can contain polyester resins and can contain organosilicon compounds. Additionally, other prior art references disclose reacting unsaturated polyesters with halosilanes to produce silylated polyesters. For example, publications (43 Paint Research Institute
Proceedings 558 , 43-53, (1974)) discloses reacting alkyl and aryl-dichlorosilanes with unsaturated polyesters to produce chlorosilane-containing polyesters. This chlorosilane-containing polyester is then reacted with water to form a silane diol. Other publications (Polymer Letters Edition 11 , 327-332,
(1973)) disclose the hydrosilanization of unsaturated polyesters with dichloromethylsilane to produce silane diols. It is desirable to produce polyester silane adhesion promoters with improved properties by Michael addition reaction of unsaturated conjugated polyesters with aminoalkylalkoxysilanes. It would also be desirable to produce polyester silane adhesion promoters suitable for reinforcing organic resins with any inorganic siliceous material, such as glass fibers and glass cloths. The present invention has a molecular weight of at least 1000 and a formula of (In the formula, R is a divalent hydrocarbon group; R ⁰ is 1
is a monovalent alkyl, aryl or aralkyl group; X is a monovalent alkoxy, hydroxy or oxy-group; y is 0 or 1; v is 1
is an integer of ~6; z is 0, 1 or 2;
a is 0 or a mole fraction ranging from 0.004 to 0.6; and b, d, and e are mole fractions ranging from 0.004 to 0.6; where d is greater than or equal to the sum of a, b, and e. ) The present invention relates to a method for producing a novel polyesteraminoalkylalkoxysilane polymer consisting of the following units. More specifically, the invention provides the formula (In the formula, R, a, b, d and e are the same as above, but the maximum value of b + e is 0.6). (wherein R ⁰ , X, y, v, and z are the same as above) is reacted with an aminoalkylalkoxysilane at a temperature of about 0°C to about 235°C,
The present invention relates to a method for producing polyesteraminoalkylalkoxysilanes encompassed by the formula by a Michael condensation reaction, which comprises producing polyesteraminoalkylalkoxysilanes. According to the present invention, the surface of the inorganic siliceous material is coated with a polymer consisting of the units of the above formula before or during bonding with the organic resin, thereby converting the inorganic siliceous material into an organic resin. It can be compatible with and adhesive to. Thus, the novel polymers consisting of units of the formula are adhesion promoters between inorganic siliceous materials and organic resins. When the inorganic siliceous material is a glass fiber or cloth, the novel polymer comprising units of the formula comprises: (a) a sizing agent or protective coating on the glass fiber or cloth; and (b) a sizing agent or protective coating on the glass fiber or cloth; It has dual utility as an adhesion promoter with resins. The polymer can be easily applied to the glass fibers or cloth in the form of a hydrolyzate from an aqueous solution. The polyester aminoalkylalkoxysilane of the present invention can be produced by Michael condensation of an aminoalkylalkoxysilane and an unsaturated conjugated polyester. Michael addition is
WJHickinbottom, Reactions of Organic
Compounds, pp. 48-55, (1957). The Michael addition reaction of the present invention can be written as: where R ⁰ is a monovalent alkyl, aryl or aralkyl group; X is a monovalent alkoxy, hydroxy or oxy-group; y is 0 or 1; v is an integer from 1 to 6; and z is 0, 1 or 2. Unsaturated conjugated polyesters useful in the present invention have a molecular weight of at least 1000 and have the formula Here, R, a, b, d and e are the same as above, but the maximum value of b+e is 0.6. It consists of units of . Typical polyfunctional organic carboxylic acids that can be used in making the unsaturated polyesters useful in making the polymers of this invention are: aliphatic dicarboxylic acids, such as maleic acid, chloromaleic acid. , dichloromaleic acid, succinic acid,
Adipic acid, sebacic acid, azelaic acid, glutaric acid, pimelic acid, malonic acid, suberic acid, itaconic acid and citraconic acid; and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and the like. Other polycarboxylic acids that can be used are "dimer acids", such as the dimer of norylic acid. Hydroxyl-containing monocarboxylic acids (eg, ricinoleic acid) can also be used. Alternatively, anhydrides of these various acids can be used to make unsaturated polyesters. Examples of dihydric alcohols that can be used to prepare the unsaturated polyester starting materials used in the process of the invention are: glycols, such as ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, xylene glycol and hexamethylene glycol; and diols, e.g.
1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 2,3-butanediol; 2-butenediol; 1,5-pentanediol; 2-ethyl-1,3-hexanediol ; and 1,3-butanediol. The amounts of the aforementioned dihydric alcohols and polyfunctional organic carboxylic acids used in the preparation of the unsaturated polyesters of the present invention are not critically limited, but are generally about 10% ~ approx.
Preference is given to using a 20% molar excess of dihydric alcohol. The reaction between carboxylic acid and dihydric alcohol to produce unsaturated polyester is
For example, it appears to proceed stepwise: (a) formation of an ester monoadduct, (b) condensation of carboxyl and hydroxyl groups to form polyester and water, and (c) Polyester chain ends transesterify to produce higher molecular weight polyester. Therefore, a wide reaction temperature range is used in the production of the polyester. A preferred temperature range for the process of reacting a polyfunctional organic carboxylic acid with a dihydric alcohol to form an unsaturated polyester is from about 100<0>C to about 250<0>C. Unsaturated polyesters useful in the process of the present invention can be used in the presence or absence of solvents such as xylene, and in the presence or absence of common transesterification catalysts such as tetra-alkyl titanates and p-toluenesulfonic acid. Can be manufactured. It is generally preferred that the unsaturated polyesters useful in the method of the invention have relatively high molecular weights of about 2000 to about 5000. Typical aminoalkylalkoxysilanes suitable for use as starting materials in the present invention are compounds of the formula: where R ⁰ is an alkyl group, for example methyl,
such as ethyl, propyl and butyl groups, or aryl groups, such as phenyl, naphthyl and tolyl groups, or aralkyl groups, such as
represents a benzyl group, etc.;
or 4, and z is 0, 1 or 2. Examples of such aminoalkylalkoxysilanes are: aminomethyltriethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylethyldiethoxysilane, gamma-aminopropylethyldiethoxysilane. Aminopropylphenyldiethoxysilane, N-beta(aminoethyl)gamma-aminopropyltrimethoxysilane, delta-aminobutyltriethoxysilane, delta-aminobutylmethyldiethoxysilane, delta-aminobutylethyldiethoxy silane, delta-aminobutylphenyldiethoxysilane, etc. Preferred aminoalkylalkoxysilanes are gamma-aminopropyltriethoxysilane and N-beta(aminoethyl)gamma-aminopropyltrimethoxysilane. Branched chain silanes (not included in the above formula), e.g.
Beta-aminoisopropyltriethoxysilane is also useful in the present invention. Examples of inorganic siliceous materials useful in the method of the invention are any solid or particulate silicon-containing materials such as silica, glass, asbestos, glass fibers, glass cloth, wollastonite, and the like. Useful organic resins include both thermoset resins, such as unsaturated polyester resins such as those described above, and thermoplastic resins. Examples of useful thermoplastic resins are: those derived from difunctional monomers and polyolefins such as polyethylene, polypropylene, polystyrene, polybutylene and polyisocyanates; halogenated polyolefins such as polyvinyl chloride, Polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene and polytrifluoropropene; substituted polyolefins,
For example, polyvinyl acetate, polyacrylonitrile, polyacrylates and polymethacrylates, such as polymethyl methacrylate and polyethyl methacrylate; polyesters, such as poly-1,4-butanediol isophthalate; polyamides, such as adipic acid and hexamethylene diamine polycarbonates, such as the reaction product of carbonyl chloride with p,p′-bishydroxyphenyldimethylmethane; cellulose ethers and esters, such as cellulose acetate and ethylcellulose; and polyacetals, such as
Polyformaldehyde. A preferred organic resin is a thermosetting unsaturated polyester resin. The method of the invention is carried out by reacting an aminoalkylalkoxysilane and an unsaturated polyester according to a Michael condensation reaction. Although the temperature for the reaction according to the method of the invention is not critically limited, the reaction may be from about 0°C to about 200°C.
It is preferable to carry out the test in A so preferred temperature range is from about 20°C to about 100°C. Room temperature is the most preferred temperature for the method of the invention. Although pressures above or below atmospheric pressure can be used in the process of the invention, atmospheric pressure is preferred unless low boiling solvents are used. Reaction times are generally less than 10 hours, but can be longer if necessary for certain purposes. The method of the invention can be carried out in the presence or absence of a solvent. The amount of solvent, if used, is not critical; its primary purpose is to facilitate handling of the reaction mixture. If used, the solvent can be water-soluble or water-insoluble depending on the intended use, provided that the solvent must not react with the unsaturated polyester or aminoalkylalkoxysilane reaction component. For example, the solvent may be a hydrocarbon, such as benzene, toluylene, pentane, etc.; or any halohydrocarbon, such as
It can be chlorobenzene or chlorotolylene; an ether, such as dibutyl ether, methyl ether of ethylene glycol, or dimethyl ether of ethylene glycol; or a nitrile, such as acetonitrile. For certain applications, such as the commercial production of sized glass fiber rovings for reinforcement of organic resins, water-soluble solvents are preferred. Other components may also be present in the reaction mixture. For example, by adding an organic acid such as acetic acid to the reaction mixture,
Cationically charged aminoalkylalkoxysilane acetate groups can be generated along the polyester silane chain. Examples of other useful organic acids are methylacetic acid, butyric acid or benzoic acid. Organic tertiary amines, such as triethylamine, tributylamine or diethylbutylamine, can also be added to the unsaturated polyester reactants prior to the Michael condensation reaction to generate terminal carboxyl anions or pendant carboxyl moieties along the polyester chain. However, in this way it can be ensured that all of the aminoalkylalkoxysilane reacts with the unsaturation of the polyester. EXPERIMENTAL The following experimental description illustrates the invention. In the description of the experiments, the following abbreviations are used: [Table] [Table] Method A: Preparation of an intermediate polyester with the structural formula [MA] _1.0 [PG] _1.1 Mechanical stirrer, heating mantle and Dean-Stark trap 2 equipped with a cooler with
423 g (4.0 moles) of maleic anhydride (“certified” grade) and 174
g of xylene ("laboratory" grade) was charged.
The mixture is stirred, heated to 90°C and maintained at 90°C until the reaction components are well dispersed, then 334g (4.4 moles) of 1,3-propylene glycol ("laboratory" grade) is rapidly added. and heated the solution to approximately 140°C while stirring. At this point, 61.7 g of water and xylene were removed from the overhead over a 6 hour period until the pot temperature was 150°C. Additional water and xylene are removed as the reaction mixture is heated to 190 °C;
It was held at that temperature for 1 hour. The total amount of water and xylene distilled off was 218.4 g. After cooling the reaction mixture to 130°C, 694 g of solvent and 0.27 g
(500 ppm) of phenothiazine was added while stirring the mixture. This mixture was pressure filtered through a 1-2 micron filter pad under an atmosphere of dry nitrogen to yield 1424 g of a clear light amber polyester solution having a viscosity of 35.0 centipoise at 25°C. did. Weight loss measurements on an aliquot of the resin solution on an aluminum pan placed in a forced draft oven at 120° C. for 1 hour showed that the resin solution had a solids content of 46.5% by weight. When analyzed, the composite structure of the polyester resin product was determined as follows: This product contained 5.30 meq/g of conjugated unsaturation compared to the calculated theoretical concentration of 5.76 meq/g. Other intermediate polyesters listed in the table were prepared in a similar manner. Method B: Preparation of polyesteraminoalkylalkoxysilane.
(flasks #1, 2 and 3)
39.0g (0.1 mol) produced using method (A) above
of solvent-diluted polyester resin. Additional solvent was added to flasks #1, 2, and 3 in amounts of 18.1 g, 14.0 g, and 9.7 g, respectively. 4.1 g (0.04 mole) of triethylamine was added to each flask and the mixture was stirred and heated to approximately 90°C.
The mixture was then cooled to about 60° C. and 11.0 g (0.05 mol) of Silane B was added to flask #1 and 7.8 g (0.035 mol) of Silane B was added to flask #1.
mol) of Silane B to flask #2 and 1.2
g (0.02 mole) of Silane B was added to flask #3. Heat all three reaction mixtures to reflux;
The reaction mixture was then refluxed for 1 hour and then cooled to room temperature. Glacial acetic acid was then added to the flasks as follows: 3.0 g (0.05 mol) of glacial acetic acid to flask #1, 2.1 g (0.035 mol) to flask #2,
Then 1.2 g (0.002 mole) was added to flask #3. The polyester silane product in flask #1 was
It had the following complex structure: [MA] _0.5 [MAS] _0.5 [PG] _1.1 A solution of 1% by weight active solids of this product in distilled water forms a somewhat hazy solution with a pH of 9.9. Addition of a small amount of acetic acid resulted in a clear aqueous solution. The polyester silane product in flask #2 was
It had the following complex structure: [MA] _0.6 [MAS] _0.4 [PG] _1.1 A solution of 1% active solids by weight of this product in distilled water formed a cloudy solution with a pH of 9.85. with acetic acid
Adjusting the pH to 3.5 resulted in a somewhat cloudy dispersion. The polyester silane product in flask #3 was
It had the following complex structure: [MA] _0.8 [MAS] _0.2 [PG] _1.1 A solution of 1% active solids by weight of this product in distilled water yielded a milky dispersion with a pH of 9.9. Adjustment of the PH to 3.5 by addition of acetic acid produced an opaque, clear dispersion. Polyester silanes for runs 2-16 and 20-39 were made in a similar manner as above. Method C: Laminated Composite Preparation and Testing 0.5% by weight aqueous solutions of polyesteraminoalkylalkoxysilanes were prepared and swatches of fiberglass fabric (JP Stevens #1581-112) were treated with these solutions. 20 pieces of finished glass cloth
Air dried for minutes and then heat set at 135°C for 2.5 minutes. A resin mixture consisting of 400 parts of polyester A, 40 parts of styrene monomer and part A of catalyst,
It was poured onto 44 inches (112 cm) of 3 mil (0.076 mm) thick Mylar film and a piece of glass cloth was placed over the resin mixture. Alternating layers of resin mixture and glass cloth were then placed on top of each other to form 12 layers. Fold mylar film and make it into resin.
After forming a bag around the glass layer and sealing the edges of the film, air bubbles were removed from the resin with a steel roller. The composite is made from a resin-glass layer,
0.125 inch (0.318 cm) for 30 minutes at 100°C
Pressed against the stop. Flexural strength testing was conducted on both dry composites and wet composites soaked in boiling water for 8 hours according to ASTM D790-71. Method D: Manufacture of pultruded rods Water-sized continuous strand glass roving (Owens Corning Fiberglass “OCF861”) was cut into 38 inches (96.5 cm).
was wrapped 22 times around a steel frame and cut to form 22 rovings approximately 6 feet (182.9 cm) long. These rovings were tied together at one end using 20 gauge copper wire to form a bundle. A resin mixture was prepared consisting of 1000 parts of Polyester A, 100 parts of styrene monomer and 10 parts of catalyst. A bunch of rovings are placed in this resin formulation.
Soaked for 30 minutes, then 0.25 inch (0.635
cm) precision hole glass tube (preei−sion−bore
It was pulled out through a glass tube. The glass tube was pretreated with a silicone resin mold release agent. The withdrawal speed is approx.
It was 3.5 inches/minute (approximately 8.9 cm/minute). Place the resulting drawer rod in a forced air oven at 100°C.
Allowed to cure for 30 minutes. Flexural strength tests were conducted on both "dry" rods and "wet" rods that were immersed in boiling water for 24 hours according to ASTM D-349-261. Method E: Physical properties of sized rovings (1) Abrasion test 50 inch (127 cm) sized rovings with appropriate formulation
A bundle of glass rovings (approximately 2000 strands/bundle) of length (a) twisted in the "figure 8 position" so that the central contact point is self-wearing, and (b) the central contact By rubbing with a tension of 192 g at a rate of 116 cycles/min at
Tested for abrasion resistance. The seconds to break of the bundle were measured. (2) Stiffness This test is a European stiffness test (DIN-
52316). In this test, 1000mm
A length of glass roving was hung over a 10 mm diameter key with a radius of curvature of 10 mm. Stiffness was measured in millimeters as the distance between the hanging ends of the roving at a point 62 mm below the support point. Example 1 Several polyester aminoalkylalkoxysilanes were prepared by Michael addition of aminoalkylalkoxysilanes to commercially available unsaturated polyesters according to Method B above. Tests were conducted on sized rovings according to Method E above using polyesteraminoalkylalkoxysilane as the adhesion promoter. Additionally, tests were conducted according to Method D to determine the effectiveness of polyesteraminoalkylalkoxysilanes as sizing agents in pultrusion rods. Polyester silanes were prepared as follows: runs 2-5 used polyester A and silane A, run 6 used polyester A and silane B, and runs 7-12 and 14 used polyester B and silane B. Run 13 uses polyesters B and C, and runs 15 and 16 use polyester C and silane B. Control experiment 1
uses polyester A without using silane,
Control experiment 17 used an unreacted mixture of polyester D and silane D, control experiment 18 used silane D and no polyester, and control experiment 19
does not use polyester and silane. The results are shown in the table below. [Table] The results reported in the table indicate that the polyester silane of the present invention was used as a glass sizing agent and as an adhesion promoter, in a control formulation consisting only of polyester (Experiment 1), in a simple unreacted mixture of polyester and silane. It is significantly more effective than the mixture (Run 17), the formulation consisting of only silane (Run 18), and the formulation without polyester and silane (Run 19). For example, the wear resistance times were 144 seconds and 144 seconds in experiments 17, 18, and 19, respectively.
Using the sizing agent of the invention from 50 seconds and 89 seconds
increased between 218 seconds (Experiment 14) and 371 seconds (Experiment 16). Thus, the self-abrasiveness of the glass fibers in the glass roving is effectively reduced by using the sizing agent of the present invention. As seen in the table, glass without sizing agent (experimental
There was a corresponding increase in the stiffness of the sized glass compared to the glass containing only silane sizing (Experiment 19) and the silane sizing agent (Experiment 18). The results reported in the table also demonstrate the effectiveness of the polyester silanes of the present invention (Runs 2-16) as adhesion promoters between the glass roving and Resin A in pultruded rods. For example, the dry bending strength of composites made using compounds of the invention (from 115.6 x 10 ³ psi in Experiment 4 to
The only composite made with Silane D as the adhesion promoter (135.0 x 10 ³ psi, Run 18) is greater than 12.94 x 10 ³ psi). The results obtained in the wet flexural strength tests are similar. Thus, the polyester silane of the present invention is effective as an adhesion promoter for glass roving-resin composites. Example 2 Several unsaturated polyesters were prepared according to Method A above and the properties of these polyesters are listed in the table below. Polyester silanes were prepared for testing using these polyesters and aminoalkylalkoxysilanes according to Method B above. Tests were conducted according to Method C to determine the performance of these polyester silanes as adhesion promoters in resin-glass fabric laminates. The formulations are as follows: Runs 20-22 used polyester silane made from polyester E and silane B; runs 23 and 24 used polyester F.
Run 25 used a polyester silane made from Polyester G and Silane B; Runs 26-28 used a polyester silane made from Polyester H and Silane B; Run 29 used a polyester made from polyester H and silane A; run 30 used a polyester silane made from polyester and silane A; run 31 used a polyester silane made from polyester J and silane A; run 32-
34 used a polyester silane made from polyester K and silane B; runs 35-36 used a polyester silane made from polyester L and silane B; and runs 37-39 used a polyester silane made from polyester M and silane B. Use silane. Control runs 40-42 use polyesters E, I, and K, respectively, and no silane. The results are listed in the table below. [TABLE] [TABLE] [TABLE] As the results in the table show, the polyester silanes of the present invention (Runs 20-38) performed well using both dry and wet bending strength tests on glass cloth/resin composites. , provides excellent bending strength. For example, the experiment of the present invention is 67.8×10 ³ psi in experiment 25.
A control experiment utilizing only unreacted polyester as an adhesion promoter and no silane gave a dry flexural strength ranging from 62.9 psi in Experiment 42 to 84.3 x 10 ³ psi in Experiment 24. ×
Dry flexural strengths ranged from 10 ³ psi to 66.6×10 ³ psi in run 40. Similarly, the inventive experiments gave wet bending strengths ranging from 36.2×10 ³ psi in experiment 29 to 70.7×10 ³ psi in experiment 31, whereas the control experiments gave
Flexural strengths ranged from 21.9×10 ³ to 22.9×10 ³ psi in experiment 40. The adhesion promoter of the present invention also exhibited high retention within the composite, ranging from 51.3% to 90.3%, compared to 34.4% to 90.3% for the control.
The retention rate was up to 34.8%. Experiments 43 and 44 Following the disclosure of US Pat. No. 3,252,825, an attempt was made to replicate Example 4 of that patent. In view of the fact that this patent does not disclose the reaction conditions for producing the polyester of Example 4,
Two different experiments were conducted to include polyesters with a relatively high degree of polymerization and polyesters with a relatively low degree of polymerization. The silane disclosed in Example 4 of this patent (alpha-aminopropyltriethoxysilane) is not commercially available and is known to those skilled in the art to be highly unstable if obtained. gamma-aminopropyltriethoxysilane was utilized for the experiments in this example. Procedure for Experiment 43 A three-necked, two-volume flask equipped with a mechanical stirrer, thermometer, nitrogen sponge, and Dean Stark trap with a water condenser on top.
212.24g (2.0mol) diethylene glycol,
148.11g (1.0 mole) of phthalic anhydride and
98.06 (1.0 mol) of maleic anhydride was charged.
0.2% by weight while stirring this mixture gently.
(0.9168 g) of p-toluenesulfonic acid catalyst was added. 3 at 200-225℃ until 9.0g of water is collected.
Heating was continued for a period of ~4 hours. The reaction mixture was then cooled to room temperature and the polyester mixture was found to be very viscous. 500ml
of diethyl ether was added to the reaction mixture. The mixture was stirred at room temperature for 30 minutes, and when stirring was stopped, the polyester diethyl ether layer was observed to separate. After heating the mixture to 70°C and removing diethyl ether, 200 g of polyester was added using a dropping funnel while stirring.
of gamma-aminopropyltriethoxysilane was added. The temperature of this mixture was maintained at 70-80°C for 1 hour. The mixture was cooled to room temperature and the product was found to be very viscous. 100g of acetic acid was added. The product was insoluble in water before and after addition of acetic acid. Method of Experiment 44 Repeat the method of Experiment 43 using the same amounts of reaction components, heating the reaction mixture to 135 °C and holding overnight;
Then water collection (27 g H ₂ O) is stopped until
Heated between 200°C and 235°C. The reaction mixture was then cooled to room temperature and 500 ml of the mixture was added while stirring.
of diethyl ether was added dropwise. After stirring for 1 hour, there was complete layer separation between the polyester and diethyl ether. After heating the mixture to 70° C. and distilling off the diethyl ether, 200 g of gamma-aminopropyltriethoxysilane were added dropwise while stirring the mixture. After all but about 25-30 grams of gamma-aminopropyltriethoxysilane had been added, the mixture gelled and became unmanageable. Even if you add 100g of acetic acid,
No change occurred in the gelation of the polyester. Run 43 used a polyester with a relatively low degree of polymerization and provided an attempted modified polyester that was insoluble in diethyl ether. This insolubility indicates that the polyester would not be useful as a forming size agent. Run 44 used a polyester with a relatively high degree of polymerization and provided a gelled polyester silane product that was also not useful as a sizing agent. Example 3 To determine the effectiveness of the polyester silane of the present invention as an adhesion promoter between wollastonite and polyester resin, a polyester resin/wollastonite composite was prepared as follows: Distillation of 2 g. Water, 25% by weight of 16 in the solvent of the Michael addition product of polyester B and silane B
g for 5 minutes with mixing. The resulting mixture was added to 400 g of wollastonite and tumbled for 30 minutes using a jar mill to produce a processed filler. Place the treated filler into a drying tray.
Dry for 60 minutes at 105°C in a forced air oven. A resin mixture was prepared consisting of 2200 parts of Polyester A, 220 parts of styrene monomer and 22 parts of catalyst. 200g of the above formulation was placed in a stainless steel bowl and the bowl was placed on a Hobart mixer equipped with a doughnut. 300 g of polyester silanized wollastonite was added to the bowl with moderate mixing and mixing continued for approximately 25 minutes until the resulting resin/filler mixture was of a uniform consistency. The resin/filler blend was molded into an 8 inch x 8 inch x 1/8 inch (20 cm x 20 cm x 0.3 cm) chrome-plated cavity mold at 100°C and 48 tons of pressure using Mylar as a mold release agent. molded for 30 minutes. The resulting composite was cooled to room temperature under pressure to prevent warping. As a comparison, a polyester resin/wollastonite composite was used above using the above method.
300g in place of 300g of treated wollastonite
manufactured using untreated filler. The initial bending strength of the polyester resin/polyester silane treated wollastonite composite is
15,800 psi and a flexural strength of 9,000 psi after wet aging according to ASTM-D-790-71, whereas the polyester resin/untreated wollastonite composite provides an initial flexural strength of 13,800 psi and a flexural strength of 6,800 psi after wet aging according to ASTM-D-790-71. provided.

Claims (1)

[Claims] 1 formula (In the formula, R is a divalent hydrocarbon group; R ⁰ is 1
is a monovalent alkyl, aryl or aralkyl group; X is a monovalent alkoxy, hydroxy or oxy-group; y is 0 or 1; v is 1
is an integer of ~6; z is 0, 1 or 2;
a is 0 or a mole fraction ranging from 0.004 to 0.6; and b, d, and e are mole fractions ranging from 0.004 to 0.6; where d is greater than or equal to the sum of a, b, and e. ) A method for producing a polyesteraminoalkylalkoxysilane consisting of units of the formula (In the formula, R, a, b, d and e are the same as above, but the maximum value of b + e is 0.6). (In the formula, R ⁰ , X, y, v, and z are the same as above) A Michael addition reaction is performed with the aminoalkylalkoxysilane represented by A method characterized by generating. 2. The method of claim 1, wherein the unsaturated conjugated polyester has a molecular weight of at least 2,000. 3 Aminoalkylalkoxysilane is gamma
2. The method of claim 1, wherein the silane is aminopropyltriethoxysilane. 4. The method according to claim 1, wherein the aminoalkylalkoxysilane is N-beta(aminoethyl)gamma-aminopropyltrimethoxysilane.