JPS631258B2 - - Google Patents

Description

[Detailed description of the invention]

The invention relates generally to reinforcing organic resins with glass fibers, and in particular to (1) "sizing" or protecting the glass fiber reinforcement, and (2) promoting adhesion between the glass fiber reinforcement and the organic resin. by means of novel compositions consisting of polyester aminoorganosilanates mixed with certain polyalkylene oxide polymers. Reinforcement of organic resins with glass fibers and the related use of organosilane adhesion promoters has been known for a long time; [e.g., U.S. Pat. No. 4,122,074]
(see issue and references therein). U.S. Pat. No. 4,122,074 (see also its division No. 4,163,073) discloses the use of certain polyesteraminoalkylalkoxysilane organic acid salts to make inorganic silicon materials in general, and glass fibers in particular, compatible with and adhesive to organic resins. It discloses that it can be done. U.S. Patent Application No. 136,362, filed April 1, 1980, discloses that salts of strong mineral acids of certain polyesteraminoalkylalkoxysilanes can be so used as well. Both US Pat. No. 3,658,571 and US Pat. No. 3,728,146 show "normal" glass size compositions containing gamma-aminopropyltriethoxysilane. In one case, the glass size composition contains a polyglycol condensate with a molecular weight of 300-400, but the reason for its presence is not clear. 2 of the handling properties of treated glass fibers intended for use as reinforcing agents in organic resins.
Two particularly important characteristics are (1) rigidity and (2) low processing agent extractability. The present invention is based on the aforementioned U.S. Patent No. 4,122,074 and U.S. Patent Application No.
It is possible to satisfy such handling characteristics by using a composition consisting of a combination of an aminoorganosilane acid salt and a certain type of polyalkylene oxide polymer as a glass fiber treatment agent, as disclosed in No. It is based on the discovery that it is possible to obtain the desired degree, ie, a discovery not suggested by the prior art. The polyester amino organosilanate that can be used in the present invention has a molecular weight greater than about 1000;
formula In the formula, R is a divalent hydrocarbon group, preferably 2 to 6
an alkylene group of carbon atoms, such as 1,2-propylene, R° is an alkyl, aryl or aralkyl group, and X is an alkoxy, hydroxy or divalent oxygen, preferably an alkoxy group of up to 8 carbon atoms, such as methoxy and ethoxy and y is 0 or 1, v is an integer from 1 to 6, z is 2, 1 or 0, preferably 0, and a is a mole fraction of 0 or preferably 0.004 to 0.6. , b and e are mole fractions ranging from 0.004 to 0.6, and d is a mole fraction ranging from 0.4 to 0.6, where d is greater than or equal to the sum of a, b and e, and An is A polymer consisting of units of a monovalent acid, preferably an anion of a strong acid such as hydrochloric acid. X is irregular hydrolysis resulting in Si-OH moieties and/or Si-O
Due to the irregular condensation resulting in -Si bonds, it can be hydroxy and/or divalent oxygen as indicated above. Such polymers are polyesters in which the valency of each available carbonyl group is satisfied by the valence of an -ORO- group or a hydroxyl group. Polyester aminoorganosilanes according to the invention can be prepared by Michael addition of a suitable aminoorganosilane to a suitable unsaturated conjugated polyester. Suitable unsaturated conjugated polyesters have at least
has a molecular weight of 1000, and the formula where R, a, b and d are as defined above. Such polyesters are readily available and can be obtained as described in US Pat. No. 4,122,074. Chain extension of such readily available polyesters with organic diisocyanates by the method detailed in U.S. Pat. Can be done. In such cases, the polyester and its acid derivatives will contain residues of such diisocyanates. Suitable aminoorganosilanes have the formula where X, R°, y, v and z are as defined above. The most preferred aminoorganosilane is gamma-aminopropyltriethoxysilane. The Michael reaction carried out in connection with the present invention is carried out as follows: a suitable unsaturated polyester resin, as described above, is dissolved in monomethyl ether of ethylene glycol and 65% by weight of this resin is dissolved in the monomethyl ether of ethylene glycol. Form a solution. Adjust the water content of this solution to 0.35%. This solution was heated to 75°C.
and maintain that temperature, then the appropriate aminoorganosilane as described above is added dropwise to the solution.
The solution is stirred during the dropwise addition of the aminoorganosilane. After all of the aminoorganosilane has been added, the solution is cooled to ambient temperature. At this point, the acid, which is anhydrous and dissolved in monomethyl ether of ethylene glycol, is added to the solution. The amount of acid used is based on all of the amino groups added to the polyester resin by reaction with aminoorganosilane,
This is the amount necessary for a complete reaction. The polyalkylene oxide polymers used according to the invention are all ethylene oxide-based polymers, all propylene oxide-based polymers or mixed ethylene oxide/propylene oxide-based polymers. They can be alkoxy-terminated. Their molecular weights can vary within a wide range as long as they are not too viscous to handle. The polyalkylene oxide polymer composition used can contain small amounts of additives such as antioxidants. _One class of polyoxyalkylene oxide polymers suitable for use in accordance with the present invention has the formula EO[ _CH2CH2O ]m[CH( _CH3 ) _CH2O ]nH where E is hydrogen or up to 8 carbon atoms. an alkyl terminal blocking group such as n-butyl, m ranges from 0 to 50, preferably up to 25, and n
~20, preferably up to 10, and m
The sum of +n must be at least 3, preferably between 3 and 35. _Ethylene oxide polymers having _{the approximate} composition _of The amount of polymer is about 10 to 100 parts by weight of polyesteraminoorganosilane.
It can be in the range of about 100 parts by weight. If the amount of polyalkylene oxide polymer is less than about 10 parts by weight per 100 parts by weight of polyesteraminoorganosilane, the effects of the present invention will be significantly reduced or lost. If the amount of the polyalkylene oxide polymer is more than about 100 parts by weight per 100 parts by weight of the polyesteraminoorganosilane, the effect of the aminoorganosilane will be reduced. 10 parts by weight of polyalkylene oxide polymer to 61.2 parts by weight of aminoorganosilane was found to be an effective ratio. The composition according to the invention comprises preparing a solution of polyesteraminoorganosilanate in monomethyl ether of ethylene glycol as described above, then determining the weight percent of polyesteraminoorganosilane in said solution, and then said weight percent Approximately 10% to approx.
It can be conveniently prepared by mixing 100% of the appropriate alkylene oxide polymer with the solution. The treatment solution according to the invention can be prepared by adding water to the composition prepared as described above or to the appropriate ratios of the individual components of the composition according to the invention with stirring to form a stable dispersion. It can be prepared. Processing solutions according to the invention preferably contain from about 1 to about 20% by weight of the composition according to the invention. The glass fiber is passed through a bath of treatment solution,
It can then be sized according to the invention by drying or "curing" it in air. Without wishing to be bound by theory, it is believed that the polyalkylene oxide polymer and polyester amino organosilanate interact as follows: (1)
During the curing process, the polyoxyalkylene polymer is oxidatively attacked to form free radicals, (2) the groups on the polyalkylene oxide are grafted onto the polyester aminoorganosilanate, and (3) 1) and (2) occur multiple times to form a cross-linked copolymer of polyalkylene oxide and polyester amino organosilanate. This cross-linked copolymer likely imparts increased stiffness to the treated glass fibers and reduces the extractability of treatment agents.
Polyoxyalkylene polymers and other materials can also be grafted onto polyester aminoorganosilanates more efficiently or at lower temperatures through the use of auxiliary substances that form or catalyze the formation of free radicals. Probably. The glass fibers treated by the method of the present invention are
Particularly suitable for use in the production of SMC (sheet molding compound) composite materials. SMC composite material is
They are generally based primarily on unsaturated polyester resins, to which are added reinforcing glass fibers, fillers, and hardeners such as oxides or hydroxides and peroxides of magnesium. EXAMPLES The following specific examples illustrate the invention. Product A Mechanical stirrer, heating mantle, addition funnel,
The solution was prepared in a 22 volume three-necked flask equipped with a thermometer attached to an automatic heating switch and a water condenser with the outlet protected by a dry nitrogen bypass. To this flask was added 14584.6 g of a polyester resin product of the formula HOCH( _CH3 )CH2O [ _C (O)CH=CHC(O) _OCH2CH ( _CH3 )O] _21H in ethylene glycol monomethyl ether. A 65% by weight solution was fed. In addition to the water already present at this stage, an additional 45g of water was added to a target level of 0.35% water by weight. This solution was heated to 75°C. 1252.5 g of gamma-aminopropyltriethoxysilane was then added dropwise to this solution over 4.75 hours with vigorous stirring. After an additional 0.5 hour at 75°C, the reaction mixture was cooled to 25°C over 2.5 hours. Then dissolved in 1.549 g of ethylene glycol monomethyl ether
206.6 g of anhydrous hydrogen chloride was added rapidly over several minutes with moderate stirring. The result is 18537.7 g of an amber-red solution (product A) containing polyesteraminopropyltriethoxysilane (61.2% by weight) present as the hydrochloride salt in monomethyl ether of ethylene glycol. Processing Solution A: First weigh 61.8 g of distilled water into a 6 oz bottle, add 30 g of Product A to it and stir for 5 minutes, then weigh 340 g of distilled water into a 16 oz bottle. , plus 60% of the dispersion of product A prepared as described in the first step.
A treatment solution containing 3 wt. Product B Average formula C ₄ H ₉ O [CH ₂ CH ₂ O] _3.7 [CH ₂ (CH ₃ )
CH ₂ O] _2.8 H polyalkylene oxide polymer to 1:2 polyalkylene oxide polymer:
The appropriate amount of product A was added to the solution in an amount calculated to yield a solid weight ratio of polyesteraminopropyltriethoxysilane hydrochloride. Processing Solution B First, weigh 50.3 g of distilled water into a 6 oz bottle, add 20 g of Product B to it, and stir for 5 minutes, then weigh 340 g of distilled water into a 16 oz bottle. , by adding thereto 60 g of the dispersion of product B prepared as described in the first step and stirring for a further 5 minutes. A treatment solution (treatment solution B) containing 3% by weight of the silane hydrochloride mixture was prepared. Products and Processing Solutions, C, D and E Products C, D and E were prepared following the procedure described for Product B, but as a polyalkylene oxide polymer, with HO(CH ₂ CH ₂ O) _4.1 H for C;
Prepared using HO(CH ₂ CH ₂ O) _13.2 H for D and HO(CH ₂ CH ₂ O) _22.3 for E, respectively. Processing solutions C, D and E were prepared following the procedure described above for processing solution B, but using products C, D and E. The following table summarizes the effect of the aforementioned treatment solutions on the roving properties of the treated fibers before and after curing. Comparing in the table the results of treatment solution A (without polyalkylene oxide polymer) and treatment solution B (similar system but containing polyalkylene oxide polymer according to the invention), it is clear that As such, glass fibers treated according to the invention are less likely to be extracted and are much stiffer than those treated with a comparable "control" system.

【table】

Table Product F 5 parts by weight of a polyalkylene oxide polymer of average formula CH ₃ O (CH ₂ CH ₂ O) _7.2 H were added to a solution of 100 parts by weight of Product A. Processing Solution F First, weigh 68.25g of distilled water into a 6 oz bottle and add 31.75g of Product F to it.
and stir for 5 minutes, then weigh 340 g of distilled water into a 16 oz bottle, add to it 60 g of the dispersion of Product F prepared as in step 1, and stir for an additional 5 minutes. A processing solution (Processing Solution F) containing 3% by weight of the polyalkyleneoxy polymer/polyesteraminopropyltriethoxysilane hydrochloride mixture prepared as described above was then prepared. Product G 10 parts by weight of a polyalkylene oxide polymer of formula CH ₃ O(CH ₂ CH ₂ O) _7.2 H were added to a solution of 100 parts by weight of Product A. Processing Solution G First, weigh 69.09g of distilled water into a 6 oz bottle and add 30.91g of Product G to it.
and by stirring for 5 minutes, then weighing 340 g of distilled water into a 16 oz bottle, adding to it 60 g of the dispersion of Product G prepared as in the first step, and stirring for an additional 5 minutes. A processing solution (Processing Solution G) containing 3% by weight of the polyalkylene oxide polymer/polyesteraminopropyltriethoxysilane hydrochloride mixture prepared above was prepared. The table reveals the effectiveness of the present invention in improving the stiffness and extraction properties of sized glass fibers.

【table】

【table】

Claims (1)

[Claims] 1. The molecular weight is greater than 1000 and the formula In the formula, R is a divalent hydrocarbon group, R゜ is an alkyl, aryl or aralkyl group, X is alkoxy, hydroxy or divalent oxygen, y is 0 or 1, and v is 1 to is an integer of 6, z is 2, 1, or 0, a is 0 or a mole fraction from 0.004 to 0.6, and b and e are
The mole fraction ranges from 0.004 to 0.6, and d is
a mole fraction in the range from 0.4 to 0.6, where d is greater than or equal to the sum of a, b and e, and An is a monovalent acid anion, and , based on 100 parts by weight of the polyester polymer in the composition, 10 to 100 parts by weight of the formula EO[ _{CH2CH2O ]} m[CH( _CH3 ) _CH2O ]nH, where E is hydrogen. or an alkyl terminal blocking group of up to 8 carbon atoms, m ranges from 0 to 50, n ranges from 0 to 20, and the sum of m+n must be at least 3. A composition for treating glass fibers, comprising a polyalkylene oxide polymer and a solvent. 2 The polyester polymer has the formula where R is an alkylene group of 2 to 6 carbon atoms, X is an alkoxy group of up to 8 carbon atoms,
and a is a mole fraction of 0.004 to 0.6, and the polyalkylene oxide polymer is an ethylene oxide polymer. 3 The polyester polymer has the formula A composition according to claim 2 consisting essentially of units of. 4 The polyalkylene oxide polymer has an average formula
A composition according to claim 3 _{having CH3O} ( _CH2CH2O ) _7.2H . 5. A composition according to claim 1, 2, 3 or 4 dispersed in a major amount of water. 6 Molecular weight is greater than 1000, formula In the formula, R is a divalent hydrocarbon group, R゜ is an alkyl, aryl or aralkyl group, X is alkoxy, hydroxy or divalent oxygen, y is 0 or 1, and v is 1 to is an integer of 6, z is 2, 1, or 0, a is 0 or a mole fraction from 0.004 to 0.6, and b and e are
The mole fraction ranges from 0.004 to 0.6, and d is
a mole fraction in the range from 0.4 to 0.6, where d is greater than or equal to the sum of a, b and e, and An is a monovalent acid anion, and , based on 100 parts by weight of the polyester polymer in the composition, 10 to 100 parts by weight of the formula EO[ _{CH2CH2O ]} m[CH( _CH3 ) _CH2O ]nH, where E is hydrogen. or an alkyl end blocking group of up to 8 carbon atoms, m ranges from 0 to 50, n ranges from 0 to 20, and the sum of m+n must be at least 3. A method for treating glass fibers comprising contacting the glass fibers with a composition comprising a polymer and a solvent dispersed in a major amount of water. 7 The polyester polymer has the formula where R is an alkylene group of 2 to 6 carbon atoms, X is an alkoxy group of up to 8 carbon atoms,
and a is a mole fraction of 0.004 to 0.6, and the polyalkylene oxide polymer is an ethylene oxide polymer. 8 The polyester polymer has the formula 8. A method according to claim 7, consisting essentially of units of. 9 The polyalkylene oxide polymer has an average formula
9. The _method of claim 8, comprising _CH3O ( _CH2CH2O ) _7.2H . 10. A method according to any of claims 6 to 9, wherein after contacting the glass fibers with the composition, the composition thus treated is dried. 11. The method according to claim 10, wherein the drying is carried out in air at high temperature. 12 Molecular weight is greater than 1000, formula In the formula, R is a divalent hydrocarbon group, R゜ is an alkyl, aryl or aralkyl group, X is alkoxy, hydroxy or divalent oxygen, y is 0 or 1, and v is 1 to is an integer of 6, z is 2, 1, or 0, a is 0 or a mole fraction from 0.004 to 0.6, and b and e are
The mole fraction ranges from 0.004 to 0.6, and d is
a mole fraction in the range from 0.4 to 0.6, where d is greater than or equal to the sum of a, b and e, and An is a monovalent acid anion, and , based on 100 parts by weight of the polyester polymer in the composition, 10 to 100 parts by weight of the formula EO[ _{CH2CH2O ]} m[CH( _CH3 ) _CH2O ]nH, where E is hydrogen. or an alkyl end blocking group of up to 8 carbon atoms, m ranges from 0 to 50, n ranges from 0 to 20, and the sum of m+n must be at least 3. Glass fibers treated by contacting them with a composition consisting of a polymer and a solvent dispersed in a major amount of water. 13 The polyester polymer has the formula where R is an alkylene group of 2 to 6 carbon atoms, X is an alkoxy group of up to 8 carbon atoms,
and a is a mole fraction of 0.004 to 0.6, and the polyalkylene oxide polymer is an ethylene oxide polymer. 14 The polyester polymer has the formula 14. The glass fiber of claim 13 consisting essentially of units of. 15. The glass fiber of claim 14, wherein said polyalkylene oxide polymer has _an average formula _CH3O ( _CH2CH2O ) _7.2H .