阅读说明：本技术 用于玻璃纤维的粘合剂组合物 (Binder composition for glass fibers ) 是由 E.M.赫尔南德兹 J.麦卡文 M.毕比 于 2020-01-09 设计创作，主要内容包括：提供了一系列用于与玻璃纤维一起使用的基于聚酯和乙烯基酯的不溶性粘合剂组合物。这些组合物包含与各种偶氮引发剂配合使用的可交联的不饱和树脂。所述组合物能够热固化、产生水,而且,其为对玻璃表现出良好粘附性的有机不溶性粘合剂。这些经热固化的粘合剂能够提供与常规的含有过氧化二苯甲酰的组合物类似的玻璃纤维抗拉强度,同时表现出改进的随时间推移的白度保留。(A series of polyester and vinyl ester based insoluble adhesive compositions for use with glass fibers are provided. These compositions comprise a crosslinkable unsaturated resin in combination with various azo initiators. The composition is capable of being thermally cured, generating water, and is an organic insoluble adhesive exhibiting good adhesion to glass. These thermally cured adhesives are capable of providing glass fiber tensile strength similar to conventional dibenzoyl peroxide-containing compositions while exhibiting improved whiteness retention over time.)

1. A fiberglass binder composition comprising:

(i) unsaturated polyester or vinyl ester resins;

(ii) an azo type initiator; and

(iii) a flow enhancer.

2. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from ortho resins.

3. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from the group consisting of ex-situ resins.

4. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from the group consisting of terephthalic resins.

5. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from the group consisting of bisphenol a fumarate.

6. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from vinyl ester resins.

7. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from fumarate resins.

8. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from maleate resins.

9. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is selected from itaconate ester resins.

10. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is present in an amount of from about 80 to about 99.8 weight percent, the sum of (i), (ii), and (iii) being 100 weight percent.

11. The composition of claim 1 wherein the unsaturated polyester or vinyl ester resin is present in an amount of from about 90 to about 99.8 weight percent, the sum of (i), (ii), and (iii) being 100 weight percent. .

12. The composition of claim 1, wherein the unsaturated polyester or vinyl ester resin is present in an amount of from about 95% to about 99.8% by weight, the sum of (i), (ii), and (iii) being 100% by weight. .

13. The composition of claim 1, wherein the azo initiator has a decomposition temperature between about 40 ° and 120 ℃.

14. The composition of claim 1 or 13, wherein the azo-type initiator is selected from the group consisting of 1,1' -azobis (cyclohexane-1-carbonitrile); 2, 2' -azobis (2-methoxybutyronitrile); 2, 2' -azobis (isobutyronitrile); 2, 2' -azobis (2, 4-dimethylvaleronitrile); 2, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile); 2, 2' -azobis (2-methylpropionic acid) dimethyl ester; 2, 2' -azobis (N-butyl-2-methylpropionamide); and 2, 2' -azobis (2-methylbutanenitrile).

15. The composition of claim 1, 13 or 14 wherein the azo-type initiator is present in an amount of from about 0.25 to about 10 weight percent, the sum of (i), (ii), and (iii) being 100 weight percent.

16. The composition of claim 1, 13 or 14 wherein the azo-type initiator is present in an amount of from about 0.25 to about 7.5 weight percent, the sum of (i), (ii), and (iii) being 100 weight percent.

17. The composition of claim 1, 13 or 14 wherein the azo-type initiator is present in an amount of from about 0.25 to about 5 weight percent, the sum of (i), (ii), and (iii) being 100 weight percent.

18. The composition of claim 1, wherein the flow enhancer is C₇-C₁₅Metal salts of fatty acids or fumed silica.

19. The composition of claim 1 or 18, wherein the flow enhancer is selected from the group consisting of zinc stearate, magnesium stearate, calcium stearate, aluminum stearate, and sodium stearate.

20. The composition of claim 1 or 18, wherein the flow enhancer is fumed silica.

21. A shaped or formed article comprising glass fibers and the composition of claim 1.

Technical Field

The present invention relates to glass fiber mat insoluble binder compositions. In particular, it relates to free radical initiated insoluble polyester and vinyl ester binder compositions for application on glass fiber mats.

Background

Most types of glass fiber mats produced require a binder to maintain the integrity of the final product. Continuous filament felt (CFM) is one such felt. This type of mat is produced by depositing a molten glass strand directly onto a moving belt in a coil (winding) manner. As the glass fibers cool, a binder is applied to the mat while the CFM hardens in place. This type of mat is most commonly used in closed molding applications such as pultrusion, vacuum infusion processing, resin transfer molding, cold forming, and the like. In contrast, Chopped Strand Mats (CSMs) are produced by cutting continuous strand rovings into short segments (segments). These fragments are then deposited on a moving belt and a binder is applied to hold the fibers together.

In general, the binder provides a way to bond the fiberglass strands to one another, resulting in a stronger material, typically with rigid structural integrity. As a general rule, the tensile strength of the glass fiber mat increases in proportion to the amount of binder added. The amount of binder placed on the glass fiber mat is proportionally controlled by the line speed for which it is determined by measuring the Limiting Organic Index (LOI). To achieve adhesive cure on a desired time scale, the amount of thermal initiator varies depending on the initial composition. The faster the production line, the more initiator is required to achieve the desired degree of cure.

For example, current insoluble binder compositions for use on continuous glass fiber mats are made primarily from polyester alkyd-type resins inherently (inrinsicaily) mixed with benzoyl peroxide. As the insoluble binder concentration on the glass fiber mat increased, more yellowing was observed. The primary reason behind the coloration (coloration) of the mat is the decomposition products of benzoyl peroxide and its ability to further oxidize the glass fiber mat and/or the materials thereon. Accordingly, there remains a need for improved adhesive compositions that provide better performance characteristics and better aesthetic properties.

Disclosure of Invention

The present invention provides improved binder compositions that can be used in conjunction with CFM type glass fiber mats. The composition comprises a curable unsaturated resin, one or more azo initiators, and a flow enhancing additive. The ingredients are then broadly combined and ground to a uniform powder having a particle size of, for example, 25 to 1000 microns, wherein the particle size is generally determined by the desired end use. The uniform powder is then applied directly, or mixed with water into a slurry, by "dusting" the glass fiber mat while it is being formed, and then applied to the mat while it is being formed. The resulting glass fiber composite structures exhibit improved whiteness over time as compared to prior compositions utilizing peroxy-type initiator systems (e.g., benzoyl peroxide).

Detailed Description

The present invention provides an adhesive composition comprising: (i) unsaturated polyester or vinyl ester resins; (ii) (ii) an azo-type initiator and (iii) a flow enhancer. In some embodiments, the unsaturated polyester or vinyl ester resin will be present in an amount of about 80 to about 99.8 weight percent, about 90 to about 99.8 weight percent, or about 95 to about 99.8 weight percent.

In general, in the compositions of the invention, the term "unsaturated polyester" will be understood to mean a polyester made from maleic anhydride, maleic acid, fumaric acid, itaconic anhydride and a diol, and/or ester derivatives of these acids with diols combined with diacids and/or anhydrides of other carboxylic acids. The vinyl ester resin and the unsaturated polyester resin used according to the invention may be selected from the unsaturated polyester resins and vinyl ester resins known to the person skilled in the art of composite materials. The composition may comprise one or a mixture of vinyl esters and/or unsaturated polyesters. Examples of suitable unsaturated polyester or vinyl ester resins to be used as base resin systems in the resins of the present invention are described by Malik et al in J.M.S. -Rev.Macromol.chem.Phys., C40(2&3), page 139-165 (2000), which can be subdivided into the following categories: (1) ortho-resin (ortho-resin): these are based on phthalic anhydride, maleic anhydride, or fumaric acid with diols, such as 1, 2-propanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, neopentyl glycol or hydrogenated bisphenol A. (2) Ectopic resin (iso-resin): these are prepared from isophthalic acid, maleic anhydride or fumaric acid with a diol. (3) Terephthalic acid resin: these are prepared from terephthalic acid, maleic anhydride or fumaric acid with glycols. Such resins also include resins in which poly (ethylene terephthalate) is used as a starting material and converted to monomers by in situ glycolysis. (4) Bisphenol a fumarate: these are based on ethoxylated bisphenol a and fumaric acid. (5) Vinyl ester resin: these are resins having unsaturated sites only at the terminal positions. For example, such unsaturation may be introduced by reaction of an epoxy resin (e.g., a glycidyl ether of bisphenol a, an epoxy of the phenol-novolac type, or an epoxy based on tetrabromobisphenol a) with (meth) acrylic acid. (6) Fumarate ester resin: these are resins derived from maleic acid, maleic anhydride, dimethyl maleate, fumaric acid, dimethyl fumarate, or diethyl fumarate with a glycol. (7) Maleate ester resin: these are resins derived from maleic acid, maleic anhydride, dimethyl maleate or diethyl maleate and a glycol. (8) Itaconate ester resin: these are resins derived from itaconic acid, itaconic anhydride, dimethyl itaconate, or diethyl itaconate with a diol.

The term "azo-type initiator" refers to a thermal radical initiator having the general formula R-N ═ N-R ', where R and R' are typically alkyl or cycloalkyl groups, optionally with other functional groups. In some embodiments, R and R' are selected fromFor example, the following groups: a cyclohexyl group; 1-cyclohexyl-1-cyano; and, C₃-C₉Alkyl, optionally substituted with cyano, amido or alkanoyl. Examples include products available from WAKO Chemicals USA, Inc. under the designations V-40, V-59, AIBN (azobisisobutyronitrile), V-65, V-70, V-601 and VAm-110, including the following compounds:

1,1' -azobis (cyclohexane-1-carbonitrile);

2, 2' -azobis (2-methoxybutyronitrile);

2, 2' -azobis (isobutyronitrile);

2, 2' -azobis (2, 4-dimethylvaleronitrile);

2, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile);

2, 2' -azobis (2-methylpropionic acid) dimethyl ester; and

2, 2' -azobis (N-butyl-2-methylpropionamide).

Further examples include trademarksThose obtained from Chemours, including52、64、67. And88 which correspond to 2-2' -azobis (2, 4-dimethylvaleronitrile), azobisisobutyronitrile, 2' -azobis (2-methylbutanenitrile), and 1,1' -azobis (cyclohexanecarbonitrile), respectively.

In some embodiments, the azo-type initiator exhibits an auto-accelerated decomposition temperature between about 40 ° and about 120 ℃. In some embodiments, the azo-type initiator is present in an amount of about 0.25 to about 10.0 wt.%, about 0.25 to about 7.5 wt.%, or about 0.25 to about 5 wt.%.

In one embodiment, the "flow enhancer" is a long chain metal salt of a fatty acid. Examples include C₇-C₁₅Zinc, calcium, and magnesium salts of fatty acids, for example, zinc stearate, magnesium stearate, calcium stearate, aluminum stearate, and the like. Additionally, the flow enhancer may be fumed silica (fumed silica), such as that sold under the trademark Evonik (R), available from EvonikThose sold under different product names. The flow enhancer is usually blended with the resin component (1) and the azo-type initiator (2) and ground into a free-flowing powder having different particle sizes.

As used herein, the term "continuous filament mat" (CFM) will be understood to mean a glass fiber mat produced by: one or more continuous glass fiber strands are wound to produce random fiber orientations. (see, e.g., U.S. patent No.7,083,855, which is incorporated herein by reference.) the glass fibers can have any known composition and class, such as those referred to as "E-glass," "a-glass," "C-glass," "D-glass," "R-glass," "S-glass," and E-glass derivatives. In one embodiment, the CFM mat is composed of E-glass (CFM mat comprises E-glass).

We have found that the compositions of the present invention are capable of bonding the different glass fiber strands making a continuous glass fiber mat, providing the necessary mechanical and aesthetic properties needed in consumer applications. The compositions provided herein meet the criteria for glass fiber manufacture needed to make suitable glass fiber mats that exhibit improved whiteness retention over time compared to existing peroxide-initiated composite structures.

For example, the compositions of the present invention may be used as binders in a variety of applications, for example, in the manufacture of glass fibre composites (including roofing tiles, insulation) and in the manufacture of felts or blankets which may then be formed into a desired shape and cured to provide a rigid three-dimensional structure. See, for example, U.S. patent No.5,393,849 and US2004/0034154, which are incorporated herein by reference.

The invention is further illustrated by the following examples of certain embodiments of the invention, but it should be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.

Experimental part

Example #1 ethylene glycol fumarate was cooked (cook) until an acid number of 40 was reached. 97.29 parts of the polyester alkyd are pulverized and inherently (inrinsically) reacted with 2.46 parts of azobisisobutyronitrile [ 2 ]64，AIBN]And 0.25 parts zinc stearate to yield example #1.

Example #2 following the above procedure, 96.87 parts of a comminuted polyester alkyd, 2.88 parts of 2, 2' -azobis (2-methylbutyronitrile), [ 2 ]67，AMBN]And 0.25 parts zinc stearate were inherently mixed to yield example #2.

Example #3 following the above procedure, 96.08 parts of a pulverized polyester alkyd, 3.67 parts of (1, 1' -azobis (cyanocyclohexane)), [ 2 ]88，ACHN]And 0.25 parts zinc stearate were inherently mixed to yield example #3.

All of the above compositions were mixed by placing the materials in a container with an epoxy liner. The vessel was then placed on a stone grinder (rock tub) for 1 hour. Thereafter, a 2% aqueous slurry was prepared from each composition. The slurry was then used to soak a piece of Uniconform mat (about 1 square foot). The soaked mats were allowed to air dry for 10 minutes and, finally, they were cured in a convection oven at 150 ℃ for a period of 10 minutes. The tensile strength of each cured mat was then determined.

TABLE #1 tensile Strength imparted to Uniconform felt Using Each composition

Testing	ASTM	(control)	Example 1	Example 2	Example 3
						Maximum tensile load of 4' fabric	D4595	106.6 pounds	57.4 pounds	59.4 pounds	83.0 pounds
Standard deviation of	D4595	7.6 pounds	10.4 pounds	12.7 pounds	21.2 pounds

The tensile strength results obtained from the cured Uniconform mat are summarized in table #1 (see above). The Uniconform mats cured using examples 1 and 2 exhibited about half the tensile strength compared to the E240-8T control. Example 3 (which contains an ACHN initiator) is able to achieve approximately 80% of the tensile strength exhibited by the control. These compositions show potential as a possible alternative to benzoyl peroxide compositions. The differences observed between examples 1-3 can be attributed to a number of factors: the low efficiency of free radical generation of azo initiators compared to dibenzoyl peroxide or Benzoperoxide (BPO), the higher water solubility of azo initiators compared to BPO, and the complexity of the process for making cured mats with these compositions.

Statement of industrial applicability

Glass fibers are a common type of fiber reinforced plastic that uses glass fibers and have wide application in water treatment, aircraft, marine, automotive, and many other industries. Its wide applicability derives in part from the fact that: it is non-magnetic, non-conductive and can be formed into complex shapes. The present invention provides improved binder compositions that can be used in conjunction with CFM type glass fiber mats. The disclosed glass fiber composite structures exhibit improved whiteness over time as compared to prior compositions utilizing peroxy-type initiator systems (e.g., benzoyl peroxide).