JPH0249017A - Preparation of polyesteraminoalkylalkoxysilane - Google Patents

Abstract

PURPOSE: To provide polyester amine alkyl alkoxy silane adequate for adhesive promoter which makes inorganic silicon material compatible and adhesive with organic resin, by reacting unsaturated conjugate polyester with amino alkyl alkoxy silane with Michael condensation.

CONSTITUTION: By reacting (A) unsaturated conjugate polyester with molecular weight more than 1000 represented by formula I (R is bivalent hydrocarbon; a is molar fraction of 0 or 0.004-0.6; b, d are molar fraction of 0.004-0.6) with (B) organic diisocyanate, polymer with molecular weight more than 5000 is provided. By reacting this polymer with (C) amino alkyl alkoxy silane represented by formula II (R0 is alkyl or others; x is alkoxy; y is 0, 1; v is 1-6; z is 0-2) at 0-235°C.

COPYRIGHT: (C)1990,JPO

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. Nos. 3.72 & 146: It is disclosed that glass fiber reinforcement of nidistomeric materials is achieved 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) U.S. 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, J IJ ester resins are mentioned (see column 4 of this patent, lines 74-75; column 5, lines 1-16). row; and Example 8)
.

[31 U.S. 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-aminoglopyltriethoxysilane to form an aqueous sizing agent (see Example 4, column 6 of this patent). .

(4) U.S. Pat. No. 3,658,571 discloses a method for reinforcing nystomeric 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 (43Pa
1nt Re5earch Institutepro
cettdings 558, 43-53 +
(1974)) disclose the reaction of 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 (poly
mer Letters Edition 11, 3
27332, (1973)) discloses 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, in part, has a molecular weight of at least 1000 and a compound of the formula is an alkoxy, hydroxy or oxy group; y is O or 1; υ is an integer from 1 to 6; 2 is 0
+ 1 or 2; ake O or 0, 004-0.
6; and d and e are approximately 0.6;
The mole fraction may range from OO4 to about 0.6; with d
is larger than, equal to, or slightly smaller than the sum of α, b, and e,
This invention relates to a novel polyesteraminoalkylalkoxysilane polymer.

Another aspect of the present invention is that the formula (wherein R is a divalent hydrocarbon group: α is 0 or O,
and b and d are mole fractions in the range of about 0.004 to about 0.6); R0 is a monovalent alkyl, aryl or aralkyl group; X is a monovalent flukoxy group; y is O or l; τ is an integer from 1 to 6; and 2 is 0
．． 1 or 2) with an aminoalkylalkoxysilane of from about 23°C to about 23°C.
The present invention relates to a process for producing polyesteraminoalkylalkoxysilanes encompassed by formula I by a Michael condensation reaction, which consists of reacting at a temperature of 5°C to form a polyesteraminoalkylalkoxysilane.

In accordance with yet another aspect of the teachings of the present invention, the surface of the inorganic siliceous material is coated with a polymer comprising units of formula (1) above before or during bonding with the organic resin. , a method of making an inorganic siliceous material compatible with and adhesive to an organic resin is provided. Thus, the novel polymers of formula I are adhesion promoters between inorganic siliceous materials and organic resins. When the inorganic siliceous material is glass fiber or cloth, the novel polymer consisting of units of formula It has dual utility as an adhesion promoter with organic resins. The polymer can be easily applied to the glass fibers or cloth in the form of a hydrolyzate from an aqueous solution.

According to another aspect of the invention, the polyester of formula (1) above is linearly chain-extended by reaction with an organic diincyanate to form the corresponding polyester aminoalkylalkoxysilane, prior to the Michael addition of the aminoalkylalkoxysilane. Can produce Shira/.

Such a process provides silylated polymers with extremely high molecular weights, greater than 5,000.

The polyester aminoalkylalkoxysilane of the present invention can be produced by Michael synthesis of aminoalkylalkoxysilane and unsaturated conjugated polyester. Michael Addition is hereby incorporated by reference, F. J. Hickinbottom.

Reactions of Organic Comp
ounds, pages 48-55, (195?). The Michael addition reaction of the present invention can be written as CCH=CHC-+ HtN(CH,CH,NF)y
(CH,)vstλ(3,)OO →-CCE CHC- NH(CH,CM,NH),(CH,)vSiX(3-
.

R'2 where Ro is a monovalent alkyl, aryl or aralkyl group; X is a monovalent alkoxy, hydroxy or oxy-group; y is 0 or l; υ is 1-6
and 2 is 0.1 or 2.

The unsaturated conjugated polyesters useful in this invention have a molecular weight of at least 1000 and consist of units of the formula: where R is a divalent hydrocarbon group; α is O or 0.
004 to 0.60 mole fraction; and b and d are mole fractions ranging from about 0.004 to about 0.6. Typical polyfunctional organic carboxylic acids that can be used in making the unsaturated polyesters useful in making the polymers of this invention are the following: aliphatic dicarboxylic acids, such as maleic acid, chloromaleic acid, etc. acids, dichloromaleic acid, succinic acid, adipic acid, sepacic acid, azelaic acid, glutaric acid, pimelic acid, malonic acid, speric acid, itaconic acid and citraconic acid; and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, such as isophthalic acid. Other polycarboxylic acids that can be used are “dimer acids”
, for example, a dimer of linoleic 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 the following nigercols, such as ethylene glycol, clopylene 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-butynediol; l, 5-bentanediol; 2-
Ethyl-1,3-hexanediol; and 1,3-butanediol.

The above-mentioned 2 used in the production of the unsaturated polyester of the present invention
Although the amounts of dihydric alcohol and polyfunctional organic carboxylic acid are not critically limited, they are generally in a molar excess of about 10% to about 20% relative to the amount of carboxylic acid used. Preference is given to using alcohol. For example, the reaction between a carboxylic acid and a dihydric alcohol to produce an unsaturated polyester appears to proceed in stages: (α) production of an ester monoadduct; (b)
Carboxyl groups and hydroxyl groups are condensed to produce polyester and water, and (C) polyester chain ends are transesterified to produce higher molecular weight polyesters. Therefore, a wide reaction temperature range is used in the production of the polyester. The preferred temperature range for the process of reacting a polyfunctional organic carboxylic acid with a dihydric alcohol to produce an unsaturated polyester is from about 00<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.

The unsaturated polyesters useful in the process of this invention are about 2
000 to about 5000,
Generally preferred. A chain-extended polymer by reacting a polyester containing hydroxyl or carboxyl end groups with an organic diisocyanate, most preferably in a ratio of at least 1 mole diincyanate to 1 mole polyester, for the purpose of producing a high molecular weight polyester. can be generated. Useful diisocyanates are any of the following and mixtures thereof: 1,6-hexamethylene diisocyanate; 1°4-tetramethylene diisocyanate; bis(2-incyanatoethyl) fumarate; l-methyl -2,4-diisocyanatocyclohexane; methylene-4,4'-diphenyl diisocyanate, commonly called MDI'; phenylene diisocyanate, e.g. 4-methoxy-1°4-
phenylene diisocyanate), 4-'700-1.3-
Phenyl diisocyanate, 4-promo 1,3-phenylene diisocyanate, 5゜6-dimethyl-1,3
-phenylene diisocyanate and 6-inpropyl-1,3-phenylene diisocyanate; 2,4-) lylene diisocyanate and 2,6-) lylene diisocyanate, mixtures of these two isomers and crude tolylene diisocyanate Incyanates include: isophorone diisocyanate; methylene-4,4'-dicyclohexyl-diincyanate; durylene diisocyanate; and other organic diisocyanates known in the polyurethane art.

A typical aminoalkylalkoxysilane suitable for use as a starting material in the present invention is a compound of the formula: H2N ((:'772CHtNHly ((?Hz
) t+ Ss etc., X represents an alkoxy group such as methoxy, ethoxy, propoxy and 2-ethylhexoxy group, y is o- or 1, ν represents an integer from 1 to 6, preferably 3 or 4, and 2 is 0, 1 or 2. Examples of such aminoalkylalkoxysilanes are: nia-aminomethyltriethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyljethoxysilane, gamma-aminopropylethyljethoxysilane, Gamma-aminopropylphenyldiethoxysilane, N-beta (aminoethyl) gamma-7
Minoglobil trimethoxysilane, delta-aminobutyltriethoxysilane, delta-aminobutylmethyljethoxysilane, delta-aminobutylethyljethoxysilane, delta-aminobutylphenyldiethoxysilane, etc.

Preferred aminoalkylalkoxysilanes are gamma-aminopropyltriethoxysilane and N-beta (aminoethyl)aminopropyltrimethoxysilane. branched chain silanes (not included in the above formula),
For example, beta-aminoisopropyltriethoxysilane is still useful in the present invention.

Examples of inorganic siliceous materials useful in the methods of the invention include:
Any solid or particulate silicon-containing material, such as silica, glass, asbestos, glass fiber, glass cloth, wollastonite, etc.

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; halodanated polyolefins such as polyvinyl chloride. , polyvinylidene chloride, polyvinylidene fluoride,
polytetrafluoroethylene and polytrifluoropropene; substituted polyolefins, such as polyvinyl acetate, polyacrylonitrile, polyacrylates and polymethacrylates, such as polymethyl methacrylate and polyethyl methacrylate; polyesters, such as poly-1,4-butanediol Inphthalates; polyamides, such as those formed from adigic acid and hexamethylene diamine; polycarnates, such as reaction products of carbonyl chloride and p,71'-bishydroxyphenyldimethylmethane; cellulose ethers and esters, tatoeha, cellulose acetate and ethylcellulose; and polyacetals, such as polyformaldehyde. Preferred organic resins are:
It 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, it is preferred that the reaction is carried out at a temperature of about 10°C to about 200°C. A more preferred temperature range is about 0°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 does not react with the unsaturated polyester or aminoalkylalkoxysilane reaction component. For example, the solvent can be a hydrocarbon, such as benzene, toluylene, pentane, etc.; it can still be any hydrocarbon, such as chlorobenzene or chlorotolylene; an ether, e.g.
It can be dibutyl ether, methyl ether of ethylene glycol, 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 bath solvents are preferred.

Other components may also be present in the reaction mixture. For example, an organic acid such as acetic acid can be added to the reaction mixture to produce cationically charged aminoalkylalkoxysilane acetate groups on the polyester silane chains. 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 terminate carboxylic anions or carboxyl anions in side groups along the polyester chain. generates a xyl site,
In this way it can be ensured that all of the aminoalkylalkoxysilane reacts with the unsaturation of the polyester.

experiment The following experimental description is 1 illustrates the invention.

In describing the experiment, the following abbreviations are used: ＼ 入入き ゆ＼＝ ト＼ ＼ ＼ cctc, tq 人 入 ＼ complete bribe injection ＼ 'l! (5(5(:l'( Q,l Mi 顯 ζ worm Mi Method l: Preparation of an intermediate polyester having the structural formula A 2J volume three-necked flask was charged with 423 t (4.0 mol) of maleic anhydride ("certified" grade) and 1742 xylene ("laboratory" grade). This mixture Stir, heat to 90°C and maintain at 90°C until the reaction components are well dispersed, then add 334f (4,4 mol) of 1,3-propylene glycol ('Laboratory grade').
was rapidly added and the solution was heated to approximately 140° C. with stirring. At this point, add 61.75' water and xylene overhead for a period of 6 hours. It was removed until the M degree reached 150°C. The reaction mixture is 190
Additional water and xylene are removed as the mixture is heated to 1-°C and held at that temperature for 1 hour. The total amount of water and xylene distilled off was 21&41. 1 of the reaction mixture
After cooling to 30 °C, solvent I of 6942 and 0.279 (
5007) 7 mL) of the 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 a clear light amber polyester solution having a viscosity of 35.0 centipoise at 25°C. It had 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 to be: Contained 2 conjugated unsaturations.

Other intermediate polyesters listed in Table 1 were produced in a similar manner.

Method B: Preparation of Polyester Aminoalkylalkoxysilane The above method was applied to each of three 250-gou three-necked flasks (flasconers 1, 2 and 3) equipped with a magnetic stirrer, a thermometer, a heating mantle and a water-cooled condenser. 3 manufactured using (a) 9. Of (0,1 mol) solvent■
- Added diluted polyester resin.

Add additional solvent ■ to flasks +1.2 and 3, 18.1 ? , 1402 and 9,72.

4.12 (Q, 04 moles) of triethylamine were added to each flask and the mixture was stirred and heated to about 90°C.

The mixture was then cooled to about 60°C and 11, of (o, o
s mol) of Silane B in flask 1, 7.89 (0
,035 mol) of Silane B in flask 2 and 1
．． 2 y (o, o 2 moles) of Silane B were added to flask +3. All three reaction mixtures were heated to reflux and the reaction mixtures were refluxed for 1 hour then cooled to room temperature. Glacial acetic acid was then added to the flask as follows:
l Ot (0.05 mol) of glacial acetic acid to 7 dicona l
Add Z I SF (0,035 mol) to +2 flasks.
and 1.2 f (0,002 mol) was added to flask 3.

The polyester silane product of Flask+1 had the following complex structure: (-M, 4]., 5 parts MIS]., 5CPG"Jl, 1
A solution of 1% active solids by weight of this product in distilled water is p
A somewhat cloudy solution of H9-9 forms. Addition of a small amount of acetic acid resulted in a clear aqueous solution.

The polyester silane product of Flask+2 had the following complex structure: (HA) CMAS'3o,4CpG]1.10.6 A solution of 1 wt% active solids of this product in distilled water was p
A cloudy solution of H9,85 was formed. Adjust pH to 3 with acetic acid
．． Adjustment to 5 resulted in a somewhat cloudy dispersion.

The polyester silane product of Flask+3 had the following complex structural formula: [Mi]CMiS]. , 2CPO''J, 10.8 A solution of 1% active solids by weight of this product in distilled water is p
A milky dispersion of H9,9 resulted. Adjustment of the pH to 3.5 by addition of acetic acid produced a opaque, clear dispersion.

In Experiments 2-16 and 20-39, f? The 1,1 ester silane was produced in a similar manner to above.

Method C Preparation and Testing of Laminated Composites 0.5 of Polyester Aminoalkylalkoxysilane
% by weight aqueous solution was prepared and swatched on glass fiber cloth (J, p, 5tevens +1581-112).
were treated with these solutions. 20 pieces of finished glass cloth
It was air-dried for a minute and then heat-set at 135°C for 25 minutes.

A resin mixture consisting of 400 parts of polyester I, 40 parts of styrene monomer, and 4 parts of Catalyst I was poured onto a 44 inch (112 cm) piece of 3 mil (0.076 mm) thick Mylar film and a piece of glass cloth was poured. was placed on the resin mixture. Alternate layers of the resin mixture and lath cloth were then placed on top of each other to form 12 layers. After the Mylar film was folded to form a bag around the resin-glass layer and the edges of the film were sealed, air bubbles were removed from the resin with a steel roller. The composite was separated from the resin-glass layer by 0.125 in.
Pressed against a stop of 0,318 cWL).

Flexural strength testing was conducted on both dry composites and wet composites soaked in boiling water for 8 hours according to ISTM D790-71.

Method D: Linear chain extension of polyester using toluene diisocyanate Polyester B was chain extended using toluene diisocyanate in the following manner: mechanical agitator, heating mantle, thermometer, and nitrogen pynoRs at the outlet. A 500-volume three-necked flask was equipped with 82 f (0.41 mol) of polyester B dissolved in 61:39% by weight of xylene:41% by weight in ethylene glycol dimethyl ether.
Added as a solid solution. While stirring the mixture at room temperature, 7, ] y (o, 0407 mol) of toluene diisocyanate (TDI) was slowly added followed by 1 v of triethylamine and the mixture was refluxed at about 108°C. After refluxing for 1-2 hours, the viscosity of the mixture increased and finally gummy lumps suddenly formed, indicating that the critical molecular weight was almost reached. At that point, the reaction was quenched by the rapid addition of 2002 ethylene glycol monomethyl ether. The mixture was heated to approximately reflux temperature and maintained at that temperature with stirring for several hours to ensure complete dissolution. The polyester product was cooled to room temperature.

Method E Production of pultruded rodsWater sized continuous strand glass rovings
(Owens Corning Fiberglass “0”
(, F861'), 38 inches (96,5 cpg)
wrapped 22 times around a steel frame and cut to approximately 6 feet (
22 rovings with a length of 18Z9(X) were formed. These rovings were tied together at one end using 2 (1") copper wire to form a bundle.

A resin mixture was prepared consisting of 1000 parts polyester, 4100 parts styrene monomer and 10 parts Catalyst I. A bundle of rovings was immersed in this resin formulation for 30 minutes and then 0.25 inch inside diameter (0,635 tx
) precision-bore glass tube
It was pulled out through a glass tube.

The glass tube was pretreated with a silicone resin mold release agent.

The withdrawal speed is approximately 3.5 inches/minute (approximately 8.9 crn 7
minutes). The resulting draw rod was placed in a forced air oven at 100° C. and 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 F: Physical Properties of Sized Roving (1) Abrasion Test Sized with appropriate formulation, 50 inches (127 cm)
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 192 at a rate of 116 cycles/min at points
Tested for abrasion resistance by rubbing with a tension of 2. The seconds to break of the bundle were measured.

(2) Stiffness This test is based on Yorotsu Guno Stiffness Test CDlN-5231.
Corresponds to 6). In this test, a glass roving of length 1000, with a diameter of 10 m and a radius of curvature of 10 m, was
I hung it on the 0ot key. Stiffness was measured in millimeters as the distance between the hanging ends of the roving at a point 62 dew 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 F above using a ester aminoalkylalkoxysilane as the adhesion promoter. Additionally, tests were conducted according to Method E to determine the effectiveness of polyesteraminoalkylalkoxysilanes as sizing agents in pultruded rods. Polyester silanes were prepared as follows: Runs 2-5 used Polyester I and Silane A, Run 6 used Polyester I and Silane B, and Runs 7-12 and 14 used Polyester B and Silane B. Run 13 used polyesters B and C, and Runs 15 and 1
6 uses polyester C and silane B. Control experiment 1 used polyester A and no 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 Run 19 uses no polyester and silane.

The results are as shown in the table ■ below.

1.74 2.22 1.74 2.85 10.4 6.0 3.2 1.6 10.4 10.4 10.4 1O04 10,4 5,2 8,0 10,4 8,7, 2Z5℃ 9.8,2: iLooC 9,8,21℃ 9.8.2ZO℃ 9,8,221)℃ 9.1,238℃ 10.4.212℃ 9.9,212℃ 103.9 12Q, 7 117.9 115.6 126.6 129.4 128.0'126.0'123.0' 11 &0" 125.0 121.0 121.0 51.3 85.3 81.9 68. 1 77.2 99.1'93.3'90.5'94.7' 98.2 18" 5.2 10.4 10.4 t 0.3 , 23.2°G 6.0 , 23. 0°C 6,2,23,5°C 123.0 121.0 125.0 135.0 98.8 83.2 79.7 80.2 91.4 118.0 1. Of sized rovings and composites Contains a sample polyester silane. This is a control experiment.

This formulation consists of an unreacted mixture of Silane D and PVIC.

, l Measured using a 0.25% by weight treatment solution of IJ ester silane.

Measurements were made using a 6.5% by weight treatment solution of polyester silane in water.

Measurements were made using a 1.0% by weight treatment solution of polyester silane in water.

Measurements were made using a 1.5% by weight treatment solution of polyester silane.

The pre-test sample was immersed in boiling water for 24 hours.

The results reported in Table I demonstrate that the polyester silanes of the present invention can be used as glass sizing agents and as adhesion promoters in control formulations consisting of only polyester (Experiment 1), in simple unreacted mixtures of polyester and silane ( Experiment 17
), the formulation from silane alone (Run 18), and the formulation without polyester and silane (Run 19). For example, the abrasion resistance times ranged from 144 seconds, 50 seconds and 89 seconds in Experiments 17.
increased between. 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 can be seen in Table 1, there was a corresponding increase in the stiffness of the sized glass compared to the glass containing no sizing agent (Run 19) and the glass containing only silane sizing agent (Run 18).

The results listed in Table ■ also show that the pultruded rondo acts as an adhesion promoter between the lath roving and resin A.
The effectiveness of the polyester silanes of the present invention (Experiments 2 to 16) is demonstrated. For example, the dry flexural strength of composites made using compounds of the invention (115.6 in Experiment 4)
X 10' psi to I'194X10'' of Experiment 6
psi) is larger than the composite made with Silane D as the adhesion promoter (135,0X10
3 psi.

Experiment 18) only. The results obtained in the wet flexural strength test are similar. Thus, the 4-liester 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 4 above and the properties of these d IJ esters are shown in Table H below.
Describe it in 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 a polyester 7 run made from polyester E and silane B; runs 23 and 24 used a 4 ester silane made from polyester F and silane B; 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 I. ; As shown in the results in Table 3, Experiment 30 was conducted using the polyester silane of the present invention (
Experiments 20 to 38) were conducted on glass cloth/resin composites.
Provides excellent flexural strength using both dry and wet flexural strength tests. For example, the experiment of the present invention is Experiment 2
A control experiment utilizing only unreacted polyester as adhesion promoter and no silane gave dry flexural strengths ranging from 67.8 xxo" psj in Experiment 5 to 84.3 X 103 p81 in Experiment 24. is 6Z9X10” psi in experiment 42 to experiment 40
gave dry flexural strengths ranging up to 66.6X10' pSi. Similarly, the experiments of the present invention ranged from 36.2×103 psj in experiment 29 to 7) in experiment 31.
? 0.7
21.9X10” in Experiment 2 to 2Z in Experiment 40
Bending up to 9X10” psi 41' 0.10Q O,100 0,100 0,100 0,033 0,033 0,033 0,035 0,020 0,050 0,050 0,013 0,014 0 ,016 0,035 0°020 o, os.

0.050 0.041 0.041 0.051 ■4.0 9.7 19.1 38.6 39.5 40.5 zO 80,8 67,9 69,9 77,9 ND3 ND3 a6 64.2 59.4 39.1 50.8 63.4 ND3 ND" 21.9 75.0 73.5 57.6 '16 81.4 DS DS 34゜4 34.4 34.8 Treatment of complex test reservoir The solution contains 0.5% by weight polyester silane in water.

The pre-test sample was immersed in boiling water for 24 hours.

Not measured.

Control experiment using only polyester and no silane as adhesion promoter.

Notes on Table H) Solution of 50 wt. polyester in Solvent I.

0.2% by weight of tetra- along with 25% by weight of xylene
Isopropyl titanate catalyst and so o ppm
of phenothiazine inhibitor by refluxing at 145°C ± 10°C for 6 hours and then at 190°C for 1 hour to remove volatile components.

0.2% by weight of tetra- along with 25% by weight of xylene
6-1 at 150 °C ± 5 °C in the presence of isopropyl titanate catalyst and 500 ppm phenothiazine inhibitor.
After refluxing for 2 hours and then at 230°C for 1 hour,
Manufactured by vacuum stripping at 30-190°C.

Absence of catalysts and inhibitors.

Not measured.

Experiment 31 used a polyester silane made from Polyester I and Silane I; Experiment 31 used a polyester silane made from Polyester J and Silane I; Experiment 3
Runs 2-34 used polyester and a polyester silane made from silane B; runs 35-36 used a polyester silane made from polyester L and silane B; and runs 37-39 made from polyester M and silane B. Use polyester silane. Control experiments 40-42 are each 4 Riztel E,! , and K without silane.

The results are listed in the table ■ below.

gave strength. Furthermore, the adhesion promoter of the present invention exhibits a high retention rate within the composite from 51.3% to 90.3%,
In comparison, the control showed a retention rate of 34.4% to 34.8%.

In accordance with the disclosure of US Patent &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 making the polyester of Example 4, two different experiments were conducted to include polyesters with relatively high degrees of polymerization and polyesters with relatively low degrees 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 when obtained. Because of this, Gamma aminoprobyl triethoxysilane was utilized for the experiments in this example.

Procedure for Experiment 43 Into a three-necked 2J flask equipped with a mechanical stirrer, a thermometer, a nitrogen sponge, and a Dean-Stark trap with a water condenser on top, 21224F (20 moles) of diethylene glycol, 148. 114 (1,0
mol] of 7-talic anhydride and 9&06 (1,0 mol)
of maleic anhydride was added. 0.2% by weight (0,9168F) of p-) while stirring the mixture gently.
A luenesulfonic acid catalyst was added. Heating was continued at 200-225° C. for a period of 3-4 hours until 9.0 y of water was collected. The reaction mixture was then cooled to room temperature and the polyester mixture was found to be very viscous. 500-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 the diethyl ether, 2001 gamma-aminopropyltriethoxysilane was added using an addition funnel while stirring the polyester. 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. 1
001 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,
The reaction mixture was heated to 135°C and held overnight, then heated to 200°C until water collection (272 H2C) stopped.
Heated to between 235°C. The reaction mixture was then cooled to room temperature and 500 rItl of diethyl ether were added dropwise while stirring the mixture. 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 diethyl ether, the mixture was heated to 200°C while stirring. The polymer aminopropyl triethoxysilane was added dropwise. Approximately 2
After all gamma-aminopropyltriethoxysilanes except 5-302 were added, the mixture glued and became unhandable.

Addition of 100F acetic acid did not change the gluing 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 7 ohming sizing agent. Run 44 used a relatively highly polymerized polyester and provided a glued polyester silane product that was also not useful as a sizing agent.

Example 3 Polyester D was chain extended using toluene diisocyanate according to the method above. Polyesteraminoalkylalkoxysilanes were "extended" using Method B
Silane B was added to Bori Ester B. Method E
Tests were conducted on resin-glass roving laminates using an "extended" polyester silane as an adhesion promoter according to the following. Additionally, tests were conducted according to Method E to determine the effectiveness of polyesteraminoalkylalkoxysilanes as sizing agents for lath roving. The results are listed in Experiment 45 in Table ■. Control experiments 46 and 47
uses a formulation consisting of a Michael addition product of silane B and "non-extending" polyester B.

The results are listed in the table ■ below.

Thorn ■ 45 B' 8 118'
88'74.6'462 B
B 110'85'77.3'47
2 B B 113' 75
'66.4' (Table TV Notes) l. Control experiment of "extended" polyester B02 produced according to the method.

3. Soak the pre-test sample in boiling water for 24 hours.

4. Measured using a 1.0% by weight aqueous solution of polyester silane.

5. Measured using a 0.5% by weight aqueous solution of polyester silane.

6 Measured using a 1.0% by weight aqueous solution of polyester silane.

As the results presented in Table ■ show, the "extended" polyester silane of Run 45 provides greater dry and wet flexural strength than that provided by the "non-extended" polyester silanes of Control Runs 46 and 47. provide. These results indicate that a direct relationship exists between increasing the molecular weight of the polyester used to make the polyester silane and increasing the effectiveness of the polyester silane as an adhesion promoter.

Example 4 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 22 Water was added to 25% by weight 16r of the Michael addition product of polyester B and silane B in vehicle 1 with mixing for 5 minutes.

The resulting mixture was added to 4007 wollastonite and tumbled for 30 minutes using a jar mill to form a treated filler. The treated filler was placed in a drying tray and dried in a forced air oven for 60 minutes at 105°C.

A resin mixture was prepared consisting of 2200 parts of polyester'%, 220 parts of styrene monomer and 22 parts of Catalyst I. 2002 of the above formulation was placed in a stainless steel bowl and the bowl was placed on a Hobart mixer equipped with a dough hook.

3002 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 uniform consistency.

Resin/filler blend 8 inches x 8 inches x l/
8 inches (20ts x 20ctn x 0.3
crn) in a chromed cavity mold.
It was molded for 30 minutes at 0°C and 48 tons of pressure using "Mylar" as a mold release agent. The resulting composite was cooled to chamber width under pressure to prevent warping.

As a comparison, a polyester resin/wollastonite composite was made using the above method using 3002 untreated raw filler in place of the 3002 treated wollastonite used above.

The polyester resin/polyester 7-run treated wollastonite composite provides an initial flexural strength of 15,800 psi and a flexural strength of 9,000 pSi after wet aging according to /ISTM-D-790-71, compared to the polyester resin The /untreated wollastonite composite provided an initial flexural strength of 800 psi and a flexural strength of 6,800 psi after wet aging.

Claims (1)

[Claims] 1. A, has a molecular weight of at least 1000, and has a formula ▲ a mathematical formula, a chemical formula, a table, etc. ▼ (wherein R is a divalent hydrocarbon group; a is 0 or 0.004 and b and d are mole fractions ranging from about 0.004 to about 0.6) with an organic diisocyanate to reduce the molecular weight. is at least 5000, and B, the chain extended unsaturated conjugated polyester has the formula ▲ Formula:
There are chemical formulas, tables, etc.▼ (In the formula, R^■ is a monovalent alkyl, aryl, or aralkyl group; X is a monovalent alkoxy group; y is 0 or 1; an integer; and z is 0, 1 or 2);
A method for producing polyester aminoalkylalkoxysilanes by Michael addition reaction, comprising reacting at a temperature of 5°C to produce polyesteraminoalkylalkoxysilanes. 2. The method according to claim 1, wherein the organic diisocyanate is toluene diisocyanate.