DE2033407A1 - Process for the production of highly transparent glass fiber reinforced laminates - Google Patents

Description

"Process for the production of highly transparent fiberglass. stronger laminates "

Priority: July 7, 1969, Italy, Ur. 19 281-A / 69

Expression -

Which means "liquid unsaturated polyester resins"

general,

man in. / Equipment of acrylic and vinyl monomers with

by polycondensation of polycarboxylic acids with polyvalent Al

y '

esters made from alcohol, the molecules of which are olefinic have unsaturated bonds. In general, unsaturated carboxylic acids, such as maleic or fumaric acid, are used in the presence of saturated carboxylic acids with a modifying effect, such as phthalic, adipic, pimelic or sebacic acid, with Glycols, such as ethylene, propylene, butylene or diethylene glycol, polycondensed. The polyester produced in this way is mixed with comonomers suitable for crosslinking from acrylic or vinyl type such as styrene, acrylonitrile or vinyl acetate.

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The curing of the unsaturated polyester resins is generally carried out with the aid of catalysts and accelerators. The most frequently used catalysts are organic peroxides ₉ which are easily soluble in the resins, in particular benzoyl-p-chlorobenzoyl and lauroyl perczido

The aforementioned unsaturated polyester resins, in combination with reinforcing materials, additives and modifiers, are suitable for a wide variety of applications ^ Z ₀ B ₀ for the production of moldings, containers; machine parts and various accessories.

There is an increasing need for flat and corrugated glass fiber reinforced laminates based on the aforementioned poly = ester resins “The unsaturated polyester resins can be used in the form described above for the aforementioned purpose. The laminates that can be produced with them have. ■ However, certain serious! laughs on »the aforementioned } Laminates in particular have a pretty bad one Transparency, flexibility, flexural strength and impact strength as well as a pronounced tendency towards water absorption

By adding certain compounds to the unsaturated polyester resins, such as methyl methacrylate and, in particular, a mixture of neopentyl glycol and tetrahydr © phthalic anhydride. the aforementioned properties, in particular the transparency, can be improved ₃ if the curing of the resins is carried out slowly at room temperature »

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However, if the curing is carried out quickly and at high temperatures becomes, the achievable transparency is quite poor.

The object of the invention was to provide a new polyester component for liquid unsaturated polyester resins and a process for the production of glass fiber-reinforced laminates which are improved

Have transparency to make available. This task is achieved by the invention.

The subject matter of the invention is thus a method for production highly transparent glass fiber reinforced laminates by impregnation the glass fiber reinforcement with a mixture of one unsaturated polyester, and an acrylic or vinyl compound as a comonomer and curing of the mass obtained, which is characterized is that a polyester resin mixture is used, which has a 3 to 15 percent by weight, based on the polyester resin mixture, Contains unsaturated polyester containing succinic acid units. - ■

With the help of the method of the invention, the aforementioned ' Difficulty using traditional methods to Sehichtstoff Manufacture can be avoided.

According to a preferred embodiment of the method of the invention a polyester resin mixture is used, which has a 5 to 10 percent by weight, based on the polyester resin mixture, Contains unsaturated polyester containing succinic acid units.

The unsaturated polyesters which can be used according to the invention are according to conventional methods by polycondensation of unsaturated Bioarboxylic acids with glycols in the presence · .. '

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of succinic acid and, if appropriate, proportionally ■ other saturated Carboxylic acids produced.

The polyester resin mixtures which can be used according to the invention are adjusted to an acid number of 5 to 50, preferably 35 to 45, based on the polyester. "Acid number ¹¹ is here to be understood as the amount of KOH (in mg) required for neutralization of 1 g resin in alcoholic solution.

The preferred "unsaturated carboxylic acid" is maleic anhydride used, while as "saturated carboxylic acid" preferred

wise phthalic anhydride is used. The preferred used Glycol is propylene glycol ",

The polyester resin mixtures which can be used according to the invention can An aromatic vinyl compound, especially styrene, in one Proportion of 25 to 50 percent by weight, preferably 35 to 45 percent by weight, based on the unsaturated polyester,. contain

th. ^. '

As glass fiber reinforcements are used to manufacture laminates P those materials are used which are generally used for such purposes. For example, fiberglass fabrics or fiberglass mats can be used or use fiberglass fleece.

According to the method of the invention, using conventional Working methods laminates are made, that one. Have transparency up to GO. The transparency is thereby called that Percentage of the light coming from a light source with constant intensity measured which the laminate and is displayed by a photoelectric cell connected to a galvanometer. "

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It was also found that the transparency of the invention Laminates produced in contrast to that of laminates made with methyl methacrylate or neopentyl glycol and unsaturated polyester resins containing tetrahydrophthalic anhydride have been produced only to a small extent

Purity depends on whether the ^{unsaturated polyester resins containing succinic acid 1} cured slowly and at room temperature or rapidly and at high temperatures during the production of the laminate

will. - - ',

The laminates made by the process of the invention also have a high mechanical strength, in particular with regard to the 'flexibility. You can get these laminates up bend to achieve a small radius of curvature without they break. The laminates produced according to the invention In addition to high impact strength and resistance to delamination, they also have a low degree of water absorption and a low weight loss. '"

The limits given above with regard to the proportion of Succinic acid are imperative as the hardness and color of the laminates are worsened when the concentration of the Succinic acid units relative to the resin becomes higher.

The use of succinic acid also provides a complete solution of the polyester component in styrene

The examples illustrate the invention.

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Ex iel 1

Man "charged a with a stirrer _φ inert gas inlet, thermometer, condenser and separator equipped for the condensate four-necked glass baskets with Pfopylenglykol, maleic anhydride and phthalic anhydride (molar ratio = 2 _S 6 s 1 s I ₉ 5) and heats it while introducing nitrogen in the mixture to 160 C. Subsequently, the temperature was gradually raised to 180 C to obtain the temperature rise controls as ₉ that the glycol loss regions is "After 2 hours Aufrechterhai = a temperature th of 180 ⁰ C is increased to the former to 200 ⁰ C. and maintains this temperature until the acid number SO and the viscosity in a TO percent toluene solution according to the 'Gardner scale has a value of 1 to K "

One then reduces the pressure in the piston _p wherein one has a schwa = chen nitrogen stream initiates _s until the resin reached an acid number of 51, and the viscosity in a TOprozentigen toluene solution according to the Gardner scale a value of T 1/2 is demonstration-to Subsequently, the The pressure is set back to the normal value, the nitrogen flow is increased, the temperature of the reaction mixture is set to 160 ° G and. stabilizers are entered. The condensation product obtained is mixed with 34 percent by weight of styrene, based on the condensation ^{product, at 100 ° C.}

The diluted ragesattigte polyester resin prepared in the aforementioned manner has a © viscosity (25 ° 0) of 650 cP and an acid number of 33 Onä is fully compatible with styrene, as well as 12 days at 65 ⁰ C "resistant. When 100 g of this poly ester resin with 0.2 ml of 6 percent cobalt octoate and 1.5 ml

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ntigiii Metbyläthyiketonperoxid treated, "the gelation time on glass" at 25 ⁰ C is 46-0 seconds. The polyester resin also has the following properties in accordance with the SPI standard (SPI = Society of the Plastics Industry, Hew York):

Gel time = 150 sec., Hardening time = 5 min., Maximum exothermic temperature = 285 G.

Ss then becomes a laminate by cold curing the aforementioned 2 polyester march produced. For this purpose, 100 parts of the resin described above are poured together with 0.2 ml G percentage cobalt octoate and 1.5 ml methyl ethyl ketone peroxide a commercially available polyester film ("Mylar"; ethylene glycol terephthalate), which has a surface weight of 120 g / m and dimensions of 30 em χ 30 cm. On the painted resin

• a .
one then places / pieces from a 450 AS glass mat with the dimensions 25 cm × 25 cm, setting a resin / glass weight ratio of about 30:70. After careful impregnation of the entire part, another polyester film corresponding to the above is placed on top of it, trapping as little air as possible. The air bubbles trapped in the impregnated part are then removed with the aid of a spatula and the entire part is allowed to cure for a few hours at room temperature. Thereafter, the temperature is raised for 1 hour at 65 ⁰ C and finally 1 additional hour at 100 ° C. .

The laminate produced in the aforementioned manner has a transparency of 20 (as defined above) and a Monoyer transparency of 0.2. The laminate also has

an Albert Koenig hardness of 171 ", a Barcol hardness of 51,

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a degree of water absorption of 1.54 ° (2 hours at 100 ° C.) and a weight loss of 0 ₉ 54 $, based on the entire laminate.

The degree of water absorption and weight loss are determined by immersion a test specimen with the dimensions 10 cm × 10 cm in boiling water for 2 hours determined »The degree of water absorption is given by the percentage weight difference of the test specimen before and after immersion in the water.

The difference in the weight of the untreated

minus
If the test specimen / that of the test specimen was immersed and then dried for 16 hours in an oven at 90 ° C., this gives the weight loss (in fo) _s

The "visibility" of the glass mat has in the case of the at room temperature If the laminate was held, the value 2, in the case of the laminate immersed in boiling water for 2 hours, the value

immersed value 3, in the case of 2 hours in boiling water / and

closing 16 hours, dried at 9O ⁰ C laminate-the value 3 and in case of 2 hours in boiling water immersed and then 24 hours at room temperature in a humid atmosphere stored laminate the value 10. The "visibility" is with a judgment of the respective laminate determined with the naked eye using a conventional scale. According to this scale, a value of 0 is assigned to a laminate that has no visibility whatsoever, and a value of 10 to a laminate with maximum visibility.

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Example 2

It becomes a laminate by high temperature hardening according to. Example 1 produced unsaturated polyester resin '. For this purpose, 100 parts of the aforementioned resin are poured together with 1.5 ml of cumene hydroperoxide to a commercially available one Polyester film (see. Example 1), which has a weight per unit area of 120 g / m and dimensions of 30 cm × 30 cm. Afterward proceed according to example 1.

The laminate produced in the aforementioned way "has a transparency of 10, an Albert Koenig hardness of 16'2",. , A Barcol hardness of 47, a Wasseraufnähmegrad of 1.39 $ and a weight loss of 0.69 i>, based on the total laminate. The visibility has initially at room temperature is 3, after 2 hours at 100 ⁰ G = 4, after 24 hours at room temperature and a value of 10 after 16 hours at 9O ⁰ C the value '. 3 ^. "·

Example '3

The procedure of Example 1 is repeated using as starting materials but propylene glycol, maleic anhydride, phthalic anhydride and succinic acid (molar ratio = 2.6 : 1: 1.12: 0.38) begins.

The polycondensation product has an acid number of 38, while the viscosity in a 70 percent toluene solution according to the Gardner scale has the value T 1/2. After a treatment as described in Example 1, it is diluted the product obtained with styrene up to a styrene content of 33 percent by weight, based on the condensation product,

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The unsaturated polyester resin obtained in the aforementioned manner has a viscosity (25 ° C.) of 640 cP and an acid number of 25 and is completely compatible with styrene and stable for 20 days at 65 ° C. If you add 100 g of this polyester resin to 0.2 ml Treat 6 percent cobalt octoate and I ₅ ml of 50 percent methyl _{ethyl ketone peroxide 9} · the gelation time on glass (25 C) is 490 seconds. The polyester resin also has the following properties according to the SP "I ₀ standard:

"Gel time = 230 seconds, hardening time = 342 seconds _os maximum exothermic temperature = ⁰

It is now made from the aforementioned polyester resin by cold curing According to Example 1, a laminate produced.

The Schichtstoff.besitzt else produced in the above-mentioned V / a transparency of 70, Albert-Koenig hardness of 168 ", a Barcol hardness of 40, a water absorption rate of 1.53 f> (in 2 hours at 100 C) and a weight loss of 0 ^ 42 #, based on the entire laminate. The visibility with regard to the glass mat initially has a value of 0 _s at room temperature, then after 2 hours at 10O ⁰ G the value 2, after 24 hours at room temperature the value 10 and after 16 Hours at 90 C the value 2.

Example 4

A laminate is produced by high-temperature hardening of the diluted unsaturated material obtained according to Example 3. Polyester resin manufactured. The procedure described in Example 2 is used,

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The in this "obtained laminate manner has a transparency of 62, Albert Koenig hardness of 153," a Barcol hardness of 45 "a Wasseraufnahmegr-ad of 1.3 Ii ⁰ and a weight loss of 0.5 ^c ß> _t based on the entire laminate. The visibility with respect to the glass mat has initially at room temperature the value 1, after 2 hours at 100 ⁰ C is 3, after 24 hours at room temperature the value 10 and aaoh 16 hours at 90 ⁰ C of 2.

Example 5

The procedure of Example 1 is repeated, but propylene glycol, maleic anhydride, Phthalic anhydride, neopentyl glycol and tetrahydrophthalic acids anhydride used in a molar ratio of 2.08: 2: 1: 2.1: 1. ■

The polycondensation product obtained has an acid number of 47 and its viscosity in a 70 percent toluene solution has the value T according to the Gardner scale. According to the usual, Treatment described in Example 1 is diluted the aforementioned product with styrene to a final Styrofoam content of 35 percent by weight, based on the condensation product.

The diluted unsaturated polyester resin thus obtained has a viscosity (25 ° C) of 400 eP and an acid number of 31 and is fully compatible with styrene and resistant to 10 days at 65 C.

If you add 100 g of the aforementioned saturated polyester resin with Ο, 2 ml of 6 percent cobalt octoate and 1.5 ml of SO percent Me-

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Treated ethyl ethyl ketone peroxide, the gelation time is up to Glass at 25 ° C for 6 minutes, the polyester resin also has the following properties in accordance with the S.P.I. standard: Gel time = 5 min., Hardening time = 5 50 sec., Maximum exothermic temperature = 156 C.

A laminate hex 'is then prepared according to Example 1 by cold curing the aforementioned polyester resin. The laminate obtained in the aforementioned manner has a transparency of 72, an Albert Koenig hardness γοη 188 ", a Barcol hardness" of 55, a degree of water absorption of 0.88 </ o (in 2 hours at 100 ° C.) and a weight loss of 0.38% , based on the total laminate. The visibility with respect to the G-lasmatte has initially at room temperature the value 0> followed by 2 hours at 100 ⁰ C.den value of 2, after 24 hours at room temperature and a value of 9 after 16 hours at 90 ⁰ C the value. 2

Example 6 ^

A laminate is produced by high-temperature curing of the unsaturated polyester resin obtained in Example 5. The procedure described in Example 2 is used.

The laminate obtained in the aforementioned manner has a transparency of 30, an Albert Koenig hardness of 172 ", a Barcol hardness of 51, a degree of water absorption of $ 0.92 and ' a weight loss of $ 0.51 based on the total Laminate. The visibility with regard to the glass mat initially has the value 1 at room temperature, then after 2 hours at 100 ° C. the value 2, after 24 hours at room temperature the value

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Value 10 and after 16 hours at 90 ⁰ C the value 2.

Example 7 .

The procedure of Example 1 is repeated, but there will be as starting materials propylene glycol, maleic anhydride and phthalic anhydride in a molar ratio of 1.58: 0.5: 1 used.

The polycondensation product obtained has an acid number of 50, and the viscosity in a 70 percent "toluene" solution has the value T 1/2 according to the Gardner scale. After customary treatment described in Example 1 is diluted the product obtained with a mixture of styrene and methyl methacrylate (Mo! Ratio '= 1: 1.15) up to a final salary of 20 percent by weight or 23 percent by weight of styrene or methyl methacrylate, based on the condensation product.

The dilute unsaturated obtained in the above manner Polyester resin has a viscosity of 90 cP and an acid number of 28 and is fully compatible with styrene as well 14 Sage at 65 ° C. resistant.

If 100 g of this polyester resin are treated with 0.2 ml of 6 percent cobalt octoate and 1.5 ml of 50 percent methyl ethyl ketone peroxide, the gelation time on glass is 52 minutes. The polyester resin also has the following properties according to the S, PI standard:

Gel time = 440 sec #, hardening time = 690 sec., Maximum exothermic temperature = 167 C.

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A laminate is now produced by cold curing the aforementioned polyester resin according to Example 1. The laminate obtained has a transparency of 66, an Altert Koenig hardness of 180 ", a Barcol hardness of 54 _t , a degree of water absorption of $ 1.57> (in 2 levels at 100 ^° C.) and a weight loss of $ 0.64 >, based on the entire laminate. the visibility with respect to the glass mat has initially at room temperature to 0, then after 2 hours at _k 100 C is 2, after 24 hours at room temperature the value and after 16 hours at 90 ⁰ C. the value 2.

B e i s ρ i el 8

A laminate is produced by high-temperature curing of the unsaturated polyester resin obtained according to Example 7, using the procedure of Example 2.

The laminate obtained in this way has a transparency of 50, an Albert Koenig hardness of 150 ", a water absorption

degree of sewing of 1.35 ^ and a weight loss of $ _{0.66> t} be ™. applied to the entire laminate. The visibility with regard to the glass mat initially has the value 1 at room temperature, then after 2 hours at 100 ^° C. the value 3, after 24 hours at room temperature the value «10 and after 16 hours at 90 ^° C. the value 2.

Example 9 '

A laminate is produced by the method of Example 1, each 100 parts of a polyester resin of the type of the resin produced in Example 1 with 0.6 ml of cumene hydroperoxide (commercial product), 0.1 ml of cobalt octoate and 1 ml

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Methyl ethyl ketone peroxide is used. The curing time at room temperature is 24 hours. ■

The laminate obtained has a flexural strength of 1450 kg / cm and a flexibility (radius of curvature when breaking the, Foil) of 10 cm.

To determine the flexibility are based on the above described way produced laminates cut out Strips with the dimensions 20 cm χ -2 cm and an average thickness of 1.5 mm wound onto cylinders with decreasing radii of curvature until breakage occurs on their surface. The flexibility, expressed in cm, represents the radius of curvature of the cylinder on which the laminate strip tested the surface fracture occurs.

Example 10

A laminate according to that described in Example 1 is obtained Process produced, however, the prepared according to Example 3, Unsaturated polyester resin containing succinic acid units is used.

0.5 ml of cumene hydroperoxide are used per 100 parts of this resin (Commercial product), 0.1 ml of cobalt octoate and 1 ml of methyl ethyl ketone peroxide are used. The curing time at room temperature is 24 hours. ■

The laminate produced in this way has a bending

2
strength of 1600 kg / cm and a flexibility of 6 cm.

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Example 11

A laminate is produced according to the method of Example 1, however, the dilute unsaturated polyester resin described in Example 5 "is used, which is made using a mixture of neopentyl glycol and tetrahydrophthalic anhydride was produced.

0.5 ml of cumene hydroperoxide are used per 100 parts of this resin (Commercial product), 0.1 ml of cobalt octoate and 1 ml of methyl ethyl ketone ^ peroxide used. The curing time at room temperature is 24 hours.

The laminate produced in this way has a bending

P.
strength of 1670 kg / cm and a flexibility of 8 cm.

Example 12

A laminate is produced according to the method of Example 1, however, the dilute unsaturated polyester resin described in Example 7 is used, which is methyl methacrylate contains.

0.5 ml of cumene hydroperoxide (commercial product), 0.1 ml of cobalt octoate and 1 ml of methyl ethyl ketone peroxide are used per 100 parts of this resin used. The curing time at room temperature is 24 hours.

The laminate produced in this way has a flexural

2
strength of 1650 kg / cm and a flexibility of 6 cm.

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Claims (8)

P a t e η t a η s ρ r ü c h e 1. Process for the production of highly transparent glass fiber reinforced Laminates by impregnating the • glass fiber reinforcement with a mixture of an unsaturated polyester . and an acrylic or vinyl compound as a comonomer and Hardening of the mass obtained, thereby marked ζ e i e h η e t that a polyester resin mixture is used which has a 3 "to 15 percent by weight, based on the polyester resin mixture, Contains unsaturated polyester containing succinic acid units. . 2. The method according to claim 1, characterized in that a polyester resin mixture is used, which has a 5 to 10 percent by weight, based on the polyester resin mixture, succinic acid units containing unsaturated polyester. 3. The method according to claim 1 or 2, characterized in that that one uses a polyester resin mixture that has an acid number from 5 to 50, preferably from 35 to 45, based on the unsaturated Polyester. 4. The method according to claim 1 to 3, characterized in that that one uses an unsaturated polyester which is produced by polycondensation a polycarboxylic acid with a polyhydric alcohol in the presence of a saturated carboxylic acid with modifying Effect has been established 5. Method according to claim 4, characterized in that; that • an unsaturated polyester is used, during its production all saturated carboxylic acid phthalic acid in the form of its anhydride t038U / 2084 became. was used. 6. The method according to claim 1 to 5, characterized in that one uses an unsaturated polyester ,, "in its Production as polycarboxylic acid maleic acid in the form of its anhy- ' drids was used. 7. The method according to claim 1 to G _9, characterized in that one uses an unsaturated polyester, used in its production as the polyhydric alcohol propylene glycol 8. The method according to claim 1 to 7, characterized in that a polyester resin mixture is used as a comonomer Styrene in a proportion of 25 to 50 percent by weight, preferably 35 to 45 percent by weight, based on the unsaturated Polyester. ORlGfNAL INSPECTED