DE1003955B - Process for the production of laminates from glass fiber material and a binder based on polyester resin - Google Patents

Description

GERMAN

The invention relates to a method for producing laminates from glass fiber material and a binder on a polyester resin basis. The polyester resin base is a mixture of a linear polyester, which still has unesterified carboxyl groups and has an acid number of 5 to 100, and a polymerizable Monomers with a terminal carbon double bond in an aliphatic radical.

The inventive method is characterized in that this mixture of polyester and monomers up to 10% of a polymerizable, vinyl group-containing silane are added that in this mass Glass fibers or glass fabric is embedded and the binder in the presence of catalysts at increased Temperature is polymerized and cured.

For many applications it is desirable to mix glass fibers with resin. The benefits that come through the incorporation of the fibers are obtained: increase in tensile strength, compressive strength and flexural strength and the impact strength of the moldings. The improvement in these properties is roughly proportional to the Amount of glass fibers incorporated into the resin; because a high glass fiber content per unit volume is very high easily obtained through the use of fiberglass mats or woven glass fabrics is the reinforcement with these the preferred method to obtain maximum strength properties.

It is known that the flexural strength and other physical properties of resin bonded Glass fiber constructions, especially glass fiber laminates, increased by a stronger bond between glass and resin will. The methods developed so far to improve the bond have been to treat the Glass fiber with means which form a film on the glass, the film being firmly bonded to the glass and the film-forming agent has reactive double bonds which are chemically with each other during curing can connect to the resin.

It has also been suggested that methacrylate chromium (III) chloride, a compound, be used as a binder on the glass fabric of the Werner type, in which methacrylic acid is coordinated with chromium, to be attached. This material is not as effective as the treating agents of the invention.

More recently (see Bj orksten et al., Modern Plastics, July 1952, pp. 124 and 188) it was shown that the treatment of glass fibers with vinyl trichlorosilane or with a Mixture of vinyltrichlorosilane with / S-chloroallyl alcohol causes a change in the surface of the fibers and thereby enables them to adhere much more firmly to the Polyester resins are bound.

The treatment of glass fibers with vinyltrichlorosilane or mixtures thereof with / J-chloroallyl alcohol is unpleasant, as a reaction product hydrogen chloride process for the production of laminates made of fiberglass material and a binder based on polyester resin

Applicant:

United States Rubber Company,
New York, NY (V. St. A.)

Representative: Dipl.-Ing. Dr.-Ing. R. Poschenrieder,
Patent attorney, Munich 8, Lucile-Grahn-Str. 38

Claimed priority:
V. St. v. America August 27, 1952 and March 19, 1953

Marvin Charles Brooks, Packanack Lake, N.J.

(V. St. A.),
has been named as the inventor

which is harmful to health and extremely harmful to textile manufacturing processes used equipment. The same inconvenience occurs when these materials are added to the resin will. The product is badly deteriorated, making the glass laminate completely unusable will.

Another method has been developed for treating glass fibers, in which the sodium salt is used by vinylsiloxanol. This salt can by reacting vinyltrichlorosilane with an aqueous Solution of sodium hydroxide can be prepared. The disadvantage of this treatment method is that the Sodium chloride and the excess of alkali contained in the treating agent are difficult to remove and that the treatment is therefore an extremely expensive process.

Other methods employ solutions of polyvinylsiloxanes in toluene in conjunction with amines as catalysts, such as triethanolamine, to the surfaces to change the fiber optics. However, this method is inconvenient because the solvent is toluene completely must be removed and then subject the tissue to very high temperatures (at least 260 °) must be in order to complete the modification reaction.

According to the invention it has been found that polymerizable vinyl group-containing silanes when they are curable Polyester resins are added in small quantities

609 838/445

those that substantially strengthen the bond that is obtained between these resins and the glass. The inventive Use of vinyl group-containing silanes is effective after aging under high humidity conditions a particularly strong improvement in the resin-glass bond. In addition, the inventive Process great practical advantages over the processes hitherto used for the same purpose

became. The particular silanes used according to the invention and containing vinyl groups are vinylalkoxysilanes, Vinyl - 2 - chloralkoxysilanes, vinylallyloxysilanes, vinylacylsilanes, where the alkoxy groups and acyl radicals each have 2 to 6 carbon atoms, or they are reaction products of a vinyl trichlorosilane with saturated aliphatic, dihydric alcohols of the following structural formula:

HO - G - 0 - Si - O - O G-OH

G -0-Si-0-O

G-OH

I. I.

G-0-Si-0-G-OH O

ι G-OH

and 540 169. As is known, the unsaturated dicarboxylic acids can partly be replaced by others dibasic acids are replaced, e.g. B. by adipic acid, succinic acid, sebacic acid, phthalic acid and Tetrachlorophthalic anhydride, which is used in amounts up to 3 moles per mole of the unsaturated dicarboxylic acid can be. Each serves as a polymerization initiator

(Here, V is the vinyl group and G is an alkylene group with at least 2 carbon atoms or a divalent one Remainder of a diglycol ether.)

The latter products are made by implementing a
Vinyl halosilane with the appropriate alcohol or the
organic acid produced. This implementation can
be effected simply by mixing the two reactants under conditions such that ² 5 known organic peroxide according to the invention can versie with liberation of hydrogen halide to react. be turned.

In this reaction, the reactants will The process of the invention for improving the

combined in such proportions that the resin-to-glass bond is economical, since only one container the alcoholic hydroxyl groups to the chlorine substance is added to the resin. This is how it is atoms in the initial reaction mixture greater than 3o much easier to carry out than the method according to the than 1 is. The vinylchlorosilane is a vinyl trichloro state of the art, in which several process stages

such as uniform coating of the glass fibers with the treatment agent, washing, hardening at the high temperature required for the treating agent on the fibers, etc. The present invention gives the manufacturer more leeway as he can easily adjust the extent of treatment to the needs of each special case. In addition, the present invention avoids complex equipment

silanes are used in which a vinyl 4 ° and process stages necessary for the pretreatment of the group directly to the silicon atom. is bound, and the glass fibers were necessary.

The amount of the silane additives to be used varies widely depending on many factors. In general, however, the amount is in the range from 0.1 to 10 percent by weight, based on the mixture of the linear polyester and monomers. Preferably 0.5 / ₀ using a Vinylhalogensilan-diol reaction product to 2 °.

The surface of the glass should be clean, i.e. that is, it must be free of any foreign material which may cause the Bonding to the resin is adversely affected. In particular, it must be free of organic material, which would adversely affect the degree of binding, especially of those organic materials which according to currency the silanes are reacted, are known 55 rend the manufacture of the glass fibers were applied Materials. They contain as a polymerization catalyst, for. B. for lubricating or sizing the fibers, an organic peroxide. As already mentioned, the The maximum effectiveness of the silane additives he contains polyester still unesterified carboxyl groups and has enough if well cleaned fibers are used, an acid number of 50 to 100. A size on the glass fibers can thereby be removed

Polyesters of this type are in US Pat. No. 60 that the glass is heated to 315 to 485 °. It is described in 2,195,362. When used, it will be known to those skilled in the art that the cleaning of these saturated linear polyesters of this type is mixed with a polymerizable monomer, e.g. B. with styrene, diallyl phthalate or triallyl cyanurate, and the mixture
is made by heating in the presence of a suitable catalytic converter
lysators hardened to the solid form. Typical curable
Mixtures of unsaturated linear polyesters and
copolymerizable monomers according to the invention
are used in U.S. Patent

silane, divinyldichlorosilane or trivinylchlorosilane, and the saturated, aliphatic dihydric alcohol is ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, Triethylene glycol or dipropylene glycol.

The silanes used according to the invention can have one to three vinyl groups directly on the silicon atom and contain one to three hydrocarbon chains bonded to the silicon atom via an oxygen atom. Preferred remainder Values of the silicon atom occupied by alkoxy, 2-chloroalkoxy and allyloxy or acyl groups are. The alkoxy, 2-chloroalkoxy and acyl groups contain 2 to 6 carbon atoms.

The following silanes are examples of the additives within the scope of the invention.

Vinyltriethoxysilane vinyltriallyloxysilane

Vinyltri- (2-chloroethoxy) -silane Vinyltri- (2-chloropropoxy) -silane

Vinyl tripropoxysilane
Vinyl tributoxysilane

Divinyldiethoxysilane Divinyldi- (2-chloroethoxy) -silane Trivinylethoxysilane Vinyltriacetoxysilane

The curable polyester resin compounds with which inven-

Temperatures either by continuous processes requiring only a few minutes or by working in batches that require 24 to 72 hours.

Example I.

The silane used in this example is the reaction product of vinyltrichlorosilane with diethylene glycol. This reaction product is known in

2,255,313 and in British Patents 540,168,70 prepared by adding 225 parts of diethylene glycol in

Table I.

Silane addition
to the resin

2 0

Flexural strength

After 3 hours

initially (kg / cm »)

4473 3885 4060 3794

in boiling water (kg / cm)

3430 1694 3605 2303

be brought to a vessel and contain 150 parts of tissue with stirring. The glass fabric used for this is

Vinyltrichlorosilane can be added. During the Zu- a long-spindle Atlas fabric manufacture with 225-1 / 3

If the silane were released, hydrogen chloride would be evolved. The warp and 225-1 / 3 weft and 57 chain ends with

The reaction mixture is then heated to 200 ° and 2 to 54 weft threads. The glass product was

Maintained at this temperature for 3 hours. The final 5-day heating to 400 ° cleaned. The total thickness

The product contains essentially no hydrolyzable chlorine. each laminate is approximately 0.3175 cm, and the glass

98 parts maleic anhydride, 148 parts phthalic acid content is approximately 64 percent by weight. Anhydride as catalyst and 163 parts of propylene glycol after working to cure the resin be heated ⁰ I ₀ benzoyl peroxide kanntem method for 3 hours at 200 ° I ¹ Iz, wherein used. The laminates are reduced by approximately 15 minutes during the last half hour. The pressure is reduced at 71 ° and then 15 minutes at 121 °. The resulting alkyd resin has hardened for an acid number for a long time. Two layers of 55 are made with each resin. 67 parts of this resin are made with 33 parts of fabric. The styrene and 1.5 parts of benzoyl peroxide in one of the laminates to form a hard resin are combined with an addition of 2% reactive, liquid casting resin. This resin is made with product; denotes Resin I used in the other laminate. 15 Resin is not changed. The results are in the

Approximately 5 to which 2 ° / ₀ of re- following table g of Resin I, compiled
action product of diethylene glycol with vinyltrichlorosilane and 1.5% benzoyl peroxide are added,

are poured onto a glass plate, one leaves to one

Film flows out and hardens under an infrared lamp. At the same time, a 5 g portion of the resin, which is 1.5 ° / "

Benzoyl peroxide catalyzed, but does not include a Silanreaktions- ^ARZ mixture cured on the same glass plate.

When fully cured, the resin films are

cracked by thermal shock. the

Observation shows that the resin film containing the silane pro-I

contains duct, has enclosed parts of the glass, where- I

against the resin film, which does not contain silane, clean and H

comes off the glass smoothly. Ή

To the effect of the polyester according to the invention

Mixtures reinforced with glass fibers to show, The numbers in Table I show that the silane addition

the flexural strength of pressed, flat foils was improved the initial flexural strength of the laminates,

tested from these mixtures. It is known that the most prominent effect of the silane

Changes in tensile strength and compressive strength in the set is the improved retention of flexural strength

generally go in parallel with the flexural strength. The 35 after aging in boiling water.

Numbers of the flexural strength were determined according to the American

Kanischen investigation procedures of the Federal Spec. their dihydric alcohols as diethylene glycol

L-P-406 a-Method 1031 obtained. also improve the flexural strength of the resin-bound ones

The method according to the invention produces a glass fabric laminate. So has z. B. a laminate that has better retention of strength properties after 40 is made with a resin that achieves conversion pro-aging in water. This property is product of vinyltrichlorosilane containing propylene glycol, measured by the flexural strength of the samples before and an initial flexural strength of 4214 kg / cm ^a and after 3 hours in boiling water after they were immersed in boiling water a flexural strength of . This aging treatment is generally 3598 kg / cm ² . A similar laminate, which does not contain any remarks as the equivalent for standing at least 45% of the action product, has been considered a much lower one month in water at room temperature. Initial flexural strength and a low flexural strength

after 3 hours in boiling water.

Example II

This example demonstrates the use of the glycolsilane reaction product in the manufacture of resin-bonded glass fabric laminates with high flexural strength. Two different polyester resins are used. One is the same as that used in example I, d. H. Resin I; the second is made as follows:

88 parts of maleic anhydride, 148 parts of phthalic anhydride, 29 parts of tetrachlorophthalic anhydride and 130 parts of ethylene glycol are heated to 220 ° for about 4 hours. The alkyd resin thus produced has a Acid number of 40. 70 parts of this resin are combined with 30 parts of styrene and 1.5 parts of benzoyl peroxide curable, liquid resin compound combined. This resin is referred to as Resin II.

The same glycolsilane reaction product as in Example I is used. This will work well in the hardenable, liquid resin mixture incorporated before it is brought into contact with the glass fabric.

Laminates made of glass fabric and polyester resin are produced, which contain up to twelve layers of glass fabric.

Example III

The example describes the production of laminates containing resins, including vinyltriethoxysilane were added.

Three resins are used to make them.

Both the resins previously referred to as Resin I and Resin II as well as Resin III are used, which consists of a mixture of 70% of a product according to Example I of the United States patent 2195 362 and 30% diallyl phthalate monomers.

Two laminates are made from each resin. 2 parts of vinyltriethoxysilane (per 100 parts of resin) are used added to a portion of the resin I. Similarly, 1 part of vinyltriethoxysilane becomes 1 part of Resin II and added to 1 part of the resin III. As a control, include those used in the second laminate of each pair Resins do not add silane.

I ¹ Ii ⁰ I ₀ cumene hydroperoxide is added as a catalyst for curing resins I and II; 1.5% benzoyl peroxide is used as a catalyst for curing resin III

added. The resin-impregnated laminates are cured by inserting the uncured laminates in a press set to a temperature of 38 °. The temperature of the press is then increased to 149 ° over the course of 30 minutes and held at 149 ° for 15 minutes. Treatment of this type will be used to ensure that the resin is fully cured regardless of the decomposition temperature of the peroxide. The decomposition temperatures the peroxides used for curing are below 149 °.

The flexural strength was determined on all laminates (Table II).

Table II

resin % Vinyl
triethoxy
silane Bend
at first
(kg / cm ² ) strength
After 3 hours
in boiling
water
(kg / cm ² ) I. 0
2 2702
4109 1253
3654 I. 0 3927 1610 II 1
0 4445
3122 3542
1526 π 1 4389 3556 Ill Ill

kernels cause an improvement in the flexural strength of laminates comparable to that which are obtained with the reaction products of dihydric alcohols and vinyl halosilane. From all organorganoxysilanes it would have to be expected that the behavior of the ayl compounds would be that of the Vinylorganoxysüane is closest comparable. The surprising fact is that even allylorganoxysilanes do not produce an improvement in flexural strength to the same extent. This is shown in the following Example explained:

Example V

Laminates similar to those in Example II with resin I are produced. A TEU of the resin are added to 1 ° / ₀ AUyltriäthoxysüan. 1% di-tert-butyldiperoxyphthalate is added to each resin. Each laminate is press cured for 15 minutes at 93 °, then 30 minutes at 149 °. The flexural strength values of the cured products are summarized in Table IV.

Table IV

resin

The numbers in Table II show that the addition of vinyltriethoxysilane to a selection of curable Polyester casting resins cause a significant improvement in the flexural strength of glass fabric laminates, especially after they have been stored in boiling water for 3 hours.

Example IV

Organoalkoxysilane

Allyl triethoxy

silanes
Vinyl triethoxy

silanes

initially (kg / cm *)

Flexural strength

After 3 hours

in boiling

water

(kg / cm ² )

4060 4130

3010 3927

This example describes the use of vinyl tripropoxysilane. Laminates are produced similarly to Example II. It will Resin I used and 2 ° / ₀ vinyltri-n-propoxysilane a Teü added thereof. Another part of Harz I remains unchanged for control purposes. I ¹ L ⁰ Io cumene hydroperoxide are added to each portion of the resin as a curing catalyst.

The figures for the flexural strength of the two laminates are summarized in Table III.

Table III

resin

° / ₀ vinyl

propoxy

silane

0
2

initially (kg / cm ² )

Flexural strength

after 3 hours in boiling water (kg / cm ² )

2702 4382

1253 3682 As can be seen from Table IV, the flexural strength is of the laminate, which contains vinyltriethoxysilane, should be stored in boiling water for approximately 3 hours 40% higher than that of the laminate, which contains AUyltriäthoxysüan.

Example VI

This example describes the use of vinyl-2-chloroalkoxysüanen, VinylaUyloxysüanen and Vinylacyloxysilanen.

Resin II is used for the production of the laminates. The laminates are made from the same glass fabric that was used in Example I. Cumene hydroperoxide (1.25%) is added as a hardening catalyst. The resin-impregnated laminates are placed in a press with a temperature of 38 ^σ . The temperature of the press is then increased to 149 ° in the course of 30 minutes and held at 149 ° for a further 15 minutes. Table V shows the physical data.

Table V

A comparison of the numbers given in Tables II and III shows that the vinyltri-n-propoxysilane is an improvement the flexural strength, which is comparable to that obtained with vinyltriethoxysilane.

It is unlikely that other organoorganoxysilanes will have the same flexural strength of laminates Improve dimensions like the vinylorganoxysilanes. For example, experience has shown that the reaction products of dihydric alcohols with cyclohexenyltrichlorosilane, Diethyldichlorosilane and amyltrichlorosilane silane additives

Vinyl triacetoxysilane
Vinyl tri-2-chloro

ethoxysilane

Vinyl triallyloxysilane
control

Parts Bend Silane at first (kg / cm ² ) 2 3962 2 4228 2 3913 0 3374

After 3 hours

in boiling

water

(kg / cm ² )

3444

3724 3591 2261

- The data in Table V show that the initial flexural strength of the cured laminates is significant is higher when resins containing a vinylacyloxysilane, a vinyl-2-chloroalkyloxysilane or a vinylacyloxysilane contain, for the manufacture of these glass fabric laminates are used as if using a laminate a resin without added silane is produced. There is a similar but more pronounced difference between the two classes of laminates after they have been aged in boiling water for 3 hours. A Comparison of the numbers in Table V with the numbers in Tables I through IV shows that the degree of improvement the flexural strength achieved by the silane addition according to the invention is approximately the same.

As previously noted, only relatively small amounts of silane are required. In the following example it is shown that even small amounts of silane such as 0.5% make very significant improvements to the laminate can be obtained.

Example VII

A series of laminates containing varying amounts of vinyltriethoxysilane is based on a similar one Kind as prepared in Example II. Resin I is used in each laminate, to which 1.25% cumene hydroperoxide to be added. The hardening is carried out in the same way as in Example III. the the exact composition of the various laminates and the obtained flexural strength figures are given in Table VI.

Table VI Table VII

Fiber surface

Arbitrated ..
ίο Finished ..
Heat cleaned
Heat cleaned

Silane Bend additive at first (kg / cm) O 2506 2 2450 O 3885 2 4473

After 3 hours

in boiling

water

(kg / cm *)

1729 1505 1694 3430

resin ° / "Vinyl
triethoxy
silane Bend
at first
(kg / cm ^a ) strength
After 3 hours
in boiling
water
(kg / cm ^a ) I. 0 2702 1253 I. 0.5
1 4893
5075 4088
4165 I. 2 4886 4165 I. 5 4732 3913 I.

The ineffectiveness of the silane additives according to the invention in a mass containing a glass fabric from which the lubricant has not been removed, is im Example VIII shown.

Example VIII

The laminates are made similar to those described in Example II, with the exception that the glass fabric used has not been subjected to any cleaning treatment, so still with the The lubricant used in its manufacture was sized. This lubricant was composed of Starch, vegetable oil, plasticizer, gelatin, vinyl polymer and an emulsifier. For comparison purposes Numbers are also given for laminates containing heat-cleaned glass fabric. The reaction product of Vinyltrichlorsüan with diethylene glycol is used as a silane additive. Harz I becomes everyone Laminates applied. The present invention is for the manufacture of Resin-bonded fiberglass constructions are applicable regardless of the arrangement of the fiberglass in the Layers. As shown in the previous examples, the process can produce fiberglass laminates which have improved flexural strength.

The present invention can be used to improve the properties of polyester compositions as well improve that with randomly oriented, crushed glass fibers z. B. with a mechanically joined Fiberglass mat are reinforced. Such a mat can be made by blowing crushed glass fibers on a movable wire screen so that the fibers are randomly arranged on the screen are. The fibers are then mechanically joined together by many barbed needles.

Another type of mat construction that can be used in the present invention is that in which the glass fibers are oriented in one direction. An ordinary resin-bonded board made from such a mat has an initial ^{flexural strength of 7462 kg / cm 2} and, after 3 hours in boiling water, a flexural strength of 5271 kg / cm ² . Flexural strength is measured by bending at right angles to the direction of fiber orientation. A similar plate containing the reaction product of vinyltrichlorosuane with diethylene glycol has an initial ^{flexural strength of 8553 kg / cm 2} and a flexural strength of 6839 kg / cm ² after 3 hours in boiling water. The improvement in flexural strength produced by the silane is evident.

The improvement of molding compounds, mainly made of polyester resins and glass fibers of short length is another example of the utility of the present invention.

Claims (6)

PATENT CLAIMS: 1. A process for the production of laminates made of glass fiber material and a binder based on polyester resin, which consists of a mixture of a linear, still unesterified carboxyl group-containing polyester with an acid number of 5 to 100 and a polymerizable monomer with a terminal carbon double bond in an aliphatic radical is, characterized in that the mixture of polyester and monomer up to 10 ° / ₀ of the reaction mass of a polymerizable vinyl groups are added having Süans be embedded in the mass of glass fiber or glass cloth, and polymerizes the binder in the presence of catalysts at elevated temperature and is cured . 2. The method according to claim 1, characterized in that a silane containing vinyl groups Vinylalkoxysüan or Vinyl-2-Chloralkoxysüan, wherein each alkoxy group contains 2 to 6 carbon atoms, or a Vinylacylsüan, wherein each acyl radical 2 to ; . ! 609 838/445 Has 6 carbon atoms, or a reaction product of a vinyltrichlorosilane with saturated aliphatic, dihydric alcohols with the following structural formula is used: HO - G - 0 - Si - O - O G-OH G —0 —Si —ΟΙ O G-OH G -0-Si--G-OH {
G-OH V == vinyl group, G = alkylene radical with at least 2 carbon atoms or a divalent radical of one Diglycol ethers. 3. The method according to claim 1 and 2, characterized in that a polyester of maleic anhydride or phthalic anhydride and propylene glycol is used. 4. The method according to claim 1 to 3, characterized in that that styrene, diallyl phthalate or triallyicyanurate is used as the polymerizable monomer. References considered: U.S. Patent No. 2,467,527. © 609 838/445 2.57