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Title:
MODIFIED WAXES AND APPLICATIONS THEREOF
Document Type and Number:
WIPO Patent Application WO/1992/007009
Kind Code:
A2
Abstract:
Waxes and polymeric waxes can graft with a coupling agent by employing a radical process. The resulted grafted waxes can be applied: 1) for coating and bonding with surfaces of materials to be applied as water-proofing antirust and reinforcing fillers; 2) as enhancing coupling agent to bond with plastics, rubber and asphalt; 3) as adhesive materials.

Inventors:
BESHAY, Alphons, D.
Application Number:
PCT/CA1991/000381
Publication Date:
April 30, 1992
Filing Date:
October 22, 1991
Export Citation:
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Assignee:
BESHAY, Alphons, D.
International Classes:
B05D7/08; C04B24/34; C04B28/02; C08F8/00; C08F289/00; C08L91/00; C08L91/06; C09D151/00; C09D191/06; C09J191/06; D06M14/00; D06M14/04; D06M14/18; D06M14/22; D06M15/227; D06M15/233; D06M15/507; D06M15/53; D06M17/00; D06N3/12; D21H19/18; (IPC1-7): C08F8/00; C08F251/00
Foreign References:
CA1269187A11990-05-15
EP0249442A21987-12-16
GB2205569A1988-12-14
US3935145A1976-01-27
Other References:
WORLD PATENTS INDEX LATEST Section Ch, Week 8932, 3 July 1989 Derwent Publications Ltd., London, GB; Class A, AN 89-231710 & JP,A,1 167 387 (MITSUBISHI KASEI CORP)
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Claims:
I claim:
1. A wax material grafts with a coupling agent by a grafting process to give coupling agent's grafted wax, to be employed as materials' surfaces' coating agent and as materials' interfacial coupling agent.
2. The wax material of claim 1 is selected from the group consisting of natural waxes and synthetic waxes, wherein the said natural waxes are derived from animal waxes, vegetable waxes and mineral waxes, wherein the said synthetic waxes are derived from polymeric waxes, polyoletheresters waxes, chlo¬ rinated naphthalenes and hydrocarbon type waxes.
3. The wax material of claim 2 is selected from paraf¬ fin wax and polypropylene wax.
4. The coupling agent of claim 1 is selected from the group consisting of silylating agents, zirconates agents, tita¬ nates agents, aluminozirconates agents, isocyanates agents and stearates agents.
5. The bonding agent of claim 4 is selected from the group consisting of gammamethacryloxypropyltrimethoxysilane, gammaaminopropyltriethoxysilane and polymethylenepolyphenyl isocyanate.
6. The grafting process of claim 1 is a radical pro¬ cess.
7. The radical process of claim 6 is carried out by the initiation of U.V. radiation, gammaradiation or a chemi¬ cal initiator.
8. The grafting process of claim 1 is carried out by an initiator selected from the group consisting of benzoyl peroxide, dicumyl peroxide, tbutyl perbenzoate, methylethyl ketoπe peroxide, ditbutyl peroxide and 2,5dimethyl2,5 SUBSTITUTE SHEET di(tbutyl perox) hexane.
9. The grafted wax material of claim 1 is additionally comprising acid anhydride.
10. The anhydride of claim 9 is maleic anhydride.
11. The grafted wax material of claim 1 is characterized by bonding with long or short cellulosic or polymeric fibers for bonding with polymeric matrix material, rubber, asphalt, paints, cement or gypsum.
12. The grafted wax material of claim 1 is characterized by bonding with inorganic filler material for bonding with poly¬ meric matrix material, rubber, asphalt, paints, pigments, cement or gypsum.
13. The grafted wax material of claim 1 is characterized by bonding with a mixture consisting of short or long cellulosic or polymeric fibers, starch or lignin and of inorganic filler material for bonding with polymeric matrix material, rubber, asphalt, paints, pigments, cement or gypsum.
14. The grafted wax of claim 1 is characterized by bon¬ ding with wood surfaces to give treated and coated wood of moisture resistance and improved dimentional stability.
15. The treated wood of claim 14 is characterized by bon¬ ding with paints and pigments.
16. The grafted wax of claim 1 is characterized by its employment as rustproofing material.
17. The grafted wax of claim 1 is characterized by its employment as adhesive material.
18. The grafted wax of claim 1 is characterized by its employment as a bonding agent for polymer blends. TE SHEET .
19. The coupling agent's grafted wax of claim 1, wherein the wax material is substituted with oil and grease. SUBSTITUTE SHEET.
Description:
MODIFIED WAXES AND APPLICATIONS THEREOF

FIELD OF THE INVENTION:

This invention relates to wax materials; more specifically, it relates to the bonded or modified waxes to be employed as better surface coatings or coupling agents. This is to improve the surface physical properties of materials or to improve the physicomechanical properties of materials or a composition there¬ of, or to be applied as adhesive materials.

BACKGROUND OF THE INVENTION:

The treatments of waxes are known in the art. In addition, the preparation of synthetic and polymeric waxes and their in¬ dustrial applications are also known in the art since long. For Example:

- The Japanese Patent No. 76,124,131, Oct. 29, 1976, teaches mixing of wax with ammonium silicate and metal oxide or hydroxide to be applied as water and alkalie resistant for building materials.

- The Japanese Patent No. 7,708,198, January 21, 1977, teaches the coating of reinforced yarns with polydimethylsilo- xane and wax.

- The Japanese Patent No. 7,763,247, May 25, 1977, teaches the recoating of oxidised wax with unsaturated monomer to give a hot-molten adhesive.

- Britt, A.D. et al, Pyrotechnology Symposium 1976, 1-D, found that the free radicals can be trapped by waxes or binders to be employed for explovies.

- The USSR Patent No. 597,666, March 15, 1978, teaches that waxes can be modified by reacting with ethylene glyco l and maleic anhydride in presence of peroxide.

- The Japanese Patent No. 95,191,704, Oct. 30, 1984, teaches the preparations of styrene grafted polyolefinic wax (e.g. PE high wax) can be applied as a released agent.

- The US Patent No. 4,444,243, April 10, teaches the

SUBSTITUTE SHEET

po l ymeric wax, e.g. maleiated PP, or sulphonated PP, im¬ prove the tensile strength and durability of mica reinforced thermoplastic composites.

- The US Patent No. 4,820,749, April 11, 1989, teaches that plastics and rubbers can be dramatically reinforced by being filled with cellulosic fibers pregrafted with silane coupling agents by radicals.

This invention is considered as a continuation of Beshay 's previous inventions (US Pats. 4,717,742 & 4,820,749;CA1,252,586& 1,269,187), dealing with grafting of coupling agents onto natural macromolecules, i.e. cellulose, lignin & starch, to reinforce plastics and rubbers. Said continuation of the instant inven¬ tion is for grafting the coupling agents onto materials of high molecular weights such as waxes, oils & proteins and applications thereof.

BRIEF DESCRIPTION OF THE INVENTION:

It has now been discovered that grafting a coupling agent onto a wax material gives a grafted wax with coupling agent; that is to be applied as improved surface treating and coating agent, interfacial coupling agent and an adhesive material.

In comparing the testing results which can be fulfilled by employing a simple process as concerns the preparation of grafted wax with a coupling agent to those results obtained by either employing the coupling agent or the wax individually or mixed together, but in absence of internal molecular bondings between each other, a remarkable great difference can be noticed due to the grafted wax.

The radical process is one of the processes for grafting wax with a bonding agent.

Hot-molten wax can be initiated by employing an initiation process to bond with a coupling agent. The resulting materials can be applied for numerous useful industrial applications.

TE SHEET

DETAILED DISCUSSION OF THE INVENTION:

The subject of the invention relates to bonded waxes and applications thereof.

One embodiment of the instant invention is to decrease the weight ratios of the consumed coupling agents and, accordingly, the effective cost.

Second embodiment is to fulfill remarkable improvements in the physical properties of the coated materials' surfaces, i.e. to have strong and durable adherence resulting in improved water and alkalie resistance and size stability under the dif¬ ferent environmental conditions.

A third embodiment is to improve the interfacial bonding strength between a composition of materials and, hence, the physicomechanical properties of the resulted composites improved accordingly.

A fourth embodiment for the instant invention is that it can be carried out in absence of any chemical solvents, which leads to time, energy and cost savings as well as being an environmental discontaminant.

A fifth embodiment of this invention is the grafted wax with a coupling agent characterized by having long-shelf life property.

The grafted waxes with a bonding agent can be employed as improved interfacial coupling agent for different materials and/ or as improved surface coating agent. That is to be applied in the known wax applications and/or in the known coupling agents applications.

For Example, as water repellents and/or as coupling agents for a wide variety of materials such as wood, cartons, paper, yarns, textiles'fabrics, cords, natural or synthetic short or long fibers, cement, concrete, gypsum, thermoplastic & ther o-

STITUTE S ET

1 1 8- E l

setting polymers, rubber, asphalt, metals, inorganic fillers or the like.

It can also be employed as a rust-proofing material for painted or non-painted steel or automobile bodies or the like.

It is also useful in the interfacial bonding of wood par¬ ticles and wood chips for manufacturing wood boards and pannels.

The polymeric waxes such as polypropylene wax and poly¬ ethylene wax or the like can graft with a coupling agent to be employed for different applications, among which are as adhesive materials, binders or as reinforcing agents for copolymers, poly¬ mer blends, polymer composites, rubber and asphalt.

The grafted wax with a coupling agent can also be applied to bond with cellulosic materials, starch, lignin, organic and/ or inorganic filler materials to reinforce synthetic thermo¬ plastic and thermosetting polymers, rubber, asphalt, cement, con¬ crete and gypsum. In addition, it can also be employed for bonding textiles, fabrics, cartons, paper, wood or cellulosic fibers with thermoplastic or thermosetting polymer films or rubber films.

As a process for grafting wax with a coupling agent, the wax is simply initiated by a radiation or chemical initiation process. The chemical initiation could be a peroxide, e.g. dicumyl peroxide which can be added to a certain weight of the hot-molten wax while stirring, followed by the addition of a certain weight of a coupling agent such as silane bonding agent, e.g. prehydrolyzed gamma-methacryloxypropyletrimethoxysilane. After a fixed time, the reactants are cooled down to be ready for being employed for said different purposes and applications.

Solvents can be employed either for wax, initiator and/or the bonding agent. The solvent can also be employed for the resulted grafted waxes and/or for some of the treated materials such as plastics or rubbers or others.

UBSTITUTE SHEET

The reaction mechanism of grafting the wax with the coup¬ ling agent is not yet exactly known, but it could be predicted that a part of the hot-molten wax can work as a free radical catching or trapping agent when solidified by cooling. The free radicals arising from the other part of the wax and from the coupling agent by the effect of the instant initiator can partially be bonded together to give covalent bonded wax with the coupling agent. In addition, the other part of the trapped radicals can bond with the molecules on the materials'surfaces to create interfacial strong bondings.

However, this invention is not limited to such materials, nor to their weight ratios; it shows its useful advantages by employing any kind of wax, oils, grease, proteins or the like.

The means for generating free radicals is preferably ac¬ complished by using a free radical catalyst, such as a peroxide (for example, t-butyl perbenzoate, dicumyl peroxide, methylethyl ketone peroxide, benzoyl peroxide, di-t-butyl peroxide and 2,5- dimethyl-2,5-di(t-butyl peroxy) hexane. A more detailed com¬ pilation of free radical initiators which may be used is set forth on pages 11-3 toll-51 of "Polymer Handbook", Inter-Science Publishers (1966) or the like.

Also the grafting process can be carried out by the ini¬ tiation effect of gamma-radiation, U.V. radiation or any other effective process for grafting the wax with a coupling agent.

The ethylenically unsaturated carboxylic acid or acid an¬ hydride could be employed as an auxiliary agent in the practice of this invention. It is preferably be a dicarboxylic acid, such as maleic acid, maleic anhydride, furmaric acid, citraconic acid, or itaconic acid. Maleic anhydride is the preferred au¬ xiliary agent. Monocarboxylic acids such as acrylic acid and methacrylic acids may also be used. Instead of maleic anhydride polymaleic anhydride, succinic anhydride or any acid/acid an¬ hydride and the like may be used.

SUBSTITUTE SHEET

The waxes that can be used in the instant invention are those derived from animal, vegetable or mineral waxes. The ani¬ mal wax such as bees wax, lanoline wax, Shellac wax, Chinese insects' wax or the like.

The vegetable wax such as Carnouba wax, Candelilla wax, Bayberry wax, sugarcane wax, Cuticle wax or the like.

The mineral waxes are those derived either from fossils or earth waxes such as Ozocerite, Ceresin and Montan or the like, or those derived from petroleum waxes, such as paraffin wax, mic- rocrystalline wax (slack or scale wax) or the like.

The synthetic wax such as polymeric waxes, e.g. ethylenic polymer wax such as polymethylene wax, polypropylene wax, poly¬ ethylene wax, polyether-esters waxes (carbowax or sorbitol) chlorinated naphthalene (Halo-wax), hydrocarbon type via Fischer- Tropsch synthesis and the like.

The coupling agents can be employed in the instant inven¬ tion, e.g. those from organic or organo-metallic nature such as abietic acid, linoleic acid, silylating agents, isocyanates, titanates, zirconates, aluminates, stearates or the like.

The silylating coupling agents are such as those described in the U.S. Patent No. 4,820,749, columns 3 and 4, or the like.

The titanates are such as those described in the Modern Plastic Encyclopedia, 1986-87, pp.128 & 130, or the like.

The isocyanates are such as polymethylenepolyphenyliso- cyanates (PMPPIC), 1,6 hexamethylene di-isocyanates and C0-(CH2) 6-NCO, 2,4 toluene di-isocyanate or their oligomers or the like.

This invention will now be furtherely described by non- limiting examples.

STITUTE SHEET

The results can be optimized by optimising the weight ratios of the materials, preparations and conditions.

EXAMPLES:

Example No. 1:

0.5g of dicumyl peroxide is added to lOOg of hot-molten and stirred paraffin wax. The stirring is continued for 5 minu¬ tes, then cooled down to be employed for the other following examples.

Example No. 2:

4g of: a) Silane A-172 "Union Carbide" (Vinyltri-(2- methoxye hoxy) silane); b) Silane A-1100 "Union Carbide" (gam a-amino- propyltriethoxysilane); or c) Polymethylenepolyphenylisocyanate (PMPPIC) is added to lOOg of hot-molten and stirred paraf¬ fin wax as per example 1, but in absence of the peroxide, then cooled down to be applied for the other following examples.

Example No. 3:

Same method of preparation as in example no. 1, in addi¬ tion to the coupling agents of example 2, to give examples 3-a, 3-b & 3-c, which can be added gradually 5 minutes after the ad¬ dition of the initiator. The stirring is continued for another 5 minutes, then left to cool down to be employed for the other following examples.

Example No. 4:

30g of waxes prepared as per examples nos. 1, 2-a & 3-a, are individually sprayed while hot-molten onto bleached cartons ( lm 2 ), then left to cool down. The coated cartons are once again subjected for coating with LLDPE film running from the laboratory film Extruder. Those coated carton samples are aged at 220°C and at 50% humidity for thirty days. The average ad¬ hesion level is tested for said samples. The testing results are as per the following table no. 1:

TABE NO . 1

Average adhesion

Cartons coated with wax level grams ~ F

Cartons coated with non-treated wax 22.34

- Wax as per Ex. No. 1 26.12

- Wax as per Ex. No. 2-a 32.11

- Wax as per Ex. No. 2-a 126.00

In this table, it is very remarkable that the adhesion of LLDPE is dramatically improved almost six times based on the non-treated waxed cartons. This is referring to the high bon¬ ding effect of the grafted paraffin wax with silane bonding agent.

Example No. 5:

Same type of preparations of Example 4, but here the car¬ ton is substituted with cotton fabrics (lι_2). The adherence forces show their maximum values by employing the wax of 3-a, i.e. the grafted wax with silane 172. The polyethylene film is strongly bonded and penetrated into the fabric fibers.

Example No. 6:

Each 5g of the hot-molten waxes of Examples 1, 2,a, b & c and 3,a,b & c are hot-molten sprayed over stirred lOOg of chemi- calthermomechanical aspen pulp. 30g of this sprayed pulp is compounded with 70g hot-molten LLDPE, ABS, PP & PVC by using laboratory mixing Brabender. Hot-compression moulding of the different resulted composite samples are prepared and tested. The testing results are demonstrated in Tables 2,3,4 & 5.

TABLE No. 2 FOR LLDPE

30g. Fiber-coated with 5. prepared waxes Stress MPa Energy KJxlO Modulus MPa as per examples Nos.

SUBSTITUTE SHEET

TABLE NO. 2 continued;

3-α 35.1 67.2 2344

2-b 19.7 24.1 3-b 498 32.4 58.1 1813

2-c 18.4 23.1 3-c 506 28.1 52.3 1790

TABLE No. FOR ABS RESIN

SUBSTITUTE SHEET

30g. Fiber-coated with % prepared waxes As per examples Nos.

40 wt. of pre- reated Tensile Stren- Flexural Mo- Notched Izod CaCo with wax prepared

_ 5_P§_.___.__B_.___._.2_i_.._._ __£_.!__MPa ___■_._!};_._.__._._._. KJ/M

Non-filled 23 2.5 0.03 1 24 2.6 0.05

2-a 27 2.7 0.17 3-a . 45 3.9 0.29

2-b 26 2.8 0.16 3-b 43 3.8 0.28

2-c 36 2.7 0.18 3-c U 3.7 0.29

TABLE No. 7

23 2.5 0.03 24 2.7 0.05 32 2.8 0.18 47 4.1 0.28

26 2.8 0.17 5 3.8 0.24

37 2.8 0.18 43 3.9 0.20

SUBSTITUTE SHEET

Example No . 7 :

As per Ex. 6, but the wood pulp is substituted with 40% of caldium carbonate and compounded with polypropylene. The testing results are demonstrated in Table No. 6.

Example No. 8:

As per Ex. 6, but the wood pulp is premixed with 10% of calcium carbonate and compounded with ABS resin. The testing results are shown in Table No. 7.

Example No. 9:

500g of spruce wood wafers of 5% humidity are well mixed by spraying with lOg of hot-molten prepared wax of Ex.l, 2-a & 3-a. lOg of BD-019 Reichold phenolic powdered resin are well mixed with the coated wood wafers, and then molded by hot pres¬ sing at 180°c for 5 minutes and at density δlOgm/m^ for obtaining board samples having thickness 11.1mm. The internal bond stren¬ gth is determined by testing specimens in tension perpendicular to the plane of the board specimens. The test was carried out according to CSA 0188 in reference to the commercial boards. The results are shown in Table 8.

TABLE NO. 8

Internal bond psi

Commercial particles board specimens 85 Treated with wax of Ex. 1 88 Treated with wax of Ex. 2-a 98 Treated with wax of Ex. 3-a 242

Example NO. 10: Polypropylene Wax as an adhesive:

Polypropylene wax is treated with 0.5% of dicumylperoxide as per Ex.l, with 4% silane 172 as per Ex. 2-a, and with both as per Ex. 3-a. Then is used to adhere aluminium/aluminium and steel/steel. The shear strength is tested and the results are demonstrated in Table No. 9.

suBsπru E SHEET

TABLE NO. 9

Shear Strength MPa

Non-treated 6.5

Treated as per Ex. 1 7.1

Treated as per Ex. 2-a 8.2

Treated as per Ex. 3-a 14.0

Example No. 11; Grafted PP Wax as a Bonding Agent:

5% w/w of the grafted polypropylene wax with silane A-172 prepared as per Ex. 10, is compounded with 30% w/w aspen pulp and 65% w/w of polypropylene. The tested results are shown in Table No. 10.

TABLE NO.10

Tensile Str. Fluxural Modulus Notched Izod MPa GPa KJ/M

Non-filled PP 23 2.5 0.03 30% wood pulp as per Ex. 11 47 3.8 2.01

Example No. 12; Water Repellency and dimentional stability of wood: Spruce wood cut in small pieces in 4 x 2 x ^ inches. The direction of the fibers are parallel to the smallest dimension. The pieces are dried at 60°c for 24 hours and then coated with 4% w/w of the hot-molten sprayed waxes of Examples Nos. 1,2-a & 3-a. The coated pieces are kept for \-l hour at 60°C. The coated wood pieces are weighed accurately and their dimensions are measured. The samples are soaked in water for 24 hours and the wood samples are left to dry at lab. temperature. The water uptake and the expansion percentage are calculated and the re¬ sults are as per Table No. 11.

TABLE NO.11

Wood Sample Water uptake after Expansion % after 1 hr. 24 hr. 1 hr. 24 hr.

Non-treated 8.2 3.1 3.5 6.5

SUBSTITUTE SHEET

TABLE NO. 11 (continued)

Various modifications and variations of the invention will be readily apparent to those skilled in the art. It is to be understood that such modifications and variations are to be in ¬ cluded within the purview of this invention and the spirit of the present claims.