US3255060A - Process of treating surfaces of shaped articles of polyacetals with camphorsulfonic acid - Google Patents

Process of treating surfaces of shaped articles of polyacetals with camphorsulfonic acid Download PDF

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Publication number
US3255060A
US3255060A US405234A US40523464A US3255060A US 3255060 A US3255060 A US 3255060A US 405234 A US405234 A US 405234A US 40523464 A US40523464 A US 40523464A US 3255060 A US3255060 A US 3255060A
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Prior art keywords
shaped articles
polyacetals
acid
camphorsulfonic acid
treating surfaces
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US405234A
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Neumann Horst
Horndler Fritz
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/14—Chemical modification with acids, their salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • C08J2359/02—Copolyoxymethylenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31—Surface property or characteristic of web, sheet or block

Definitions

  • shaped articles which are under stress can be treated with a mixture containing p-toluene-sulfonic acid.
  • the shaped article is dipped for 10-30 seconds into an agitated mixture of 75120 C. consisting of 0.3% by weight of ptoluene-sulfonic acid, 96.2% by weight of perchloroethylene, 3.0% by weight of dioxane and 0.5% by weight of kieselguhr, then placed for 1 minute in a furnace having a temperature of 120 C., rinced with water and dried in the air. After said treatment the surface of the articles can be bonded and lacquered.
  • the present invention provides a process for improving the property of being bonded and lacquered of surfaces of shaped articles of polyacetals which comprises contacting the dry surface for a period of time ranging from 15 seconds to 30 minutes at 70150 C. with dry pulverulent camphor-sulfonic acid. After the removal of the loosely adhering acid, for example by blowing it off with air, the surface of the shaped article of polyacetal has a uniformly mat appearance, it can be wetted with water Patented June 7, 1966 and has a good bonding strength for adhesives and lacquers. It is especially advantageous that according to the process of the invention shaped articles with strong latent stress can be treated without heat treatment or other pretreatment. Moreover, parts of the surface can be covered and thus readily protected against the action of the acid. Panels, for example can be treated on one side only or parts can be protected by covering them with adhesive foils.
  • camphor-sulfonic acid Owing to the fact that camphor-sulfonic acid does practically not decompose at high temperatures, it can repeatedly be used for the surface treatment of shaped articles of polyacetals. It is possible to effect a dry treatment of the surfaces of plastics also with p-toluenesulfonic acid. However, it is disadvantageous that. the latter acid decomposes during the first use and must be washed off with water.
  • any kind of shaped articles of polyacetals can be treated.
  • polyacetals there are to be understood homopolymers of formaldehyde or trioxane and the copolymers thereof with cyclic ethers of the formula in which R andR stand for hydrogen or low molecular weight alkyl radicals, or low molecular weight, halogensubstituted alkyl radicals, and R represents a methylene, an oxymethylene, or a low molecular weight alkylor halogen-a1kyl-substituted methylene or a low molecular weight alkylor halogen-alkyl-substituted oxymethylene radical and n is one of the numbers 0,' 1, 2, and 3.
  • polyacetals such as polyoxy-methylenes the terminal groups of which may have been esterified or etherified.
  • Example 1 Pulverulent camphor-sulfonic acid was spread on panels of polyoxymethylene by means of a fine-meshed sieve in a manner such that the surface was uniformly covered. The covered panels were then heated for 3 minutes at 120 C. After having removed the powder and washed otf the adhering traces of acid with water, the panels dried in air had a mat surface. They could be bonded with one another and with panels of wood, iron and other plastic materials by means of polyisocyanate/polyester adhesive. The adhesive joints had a tensile shear strength of kp./cm., whereas untreated polyoxymethylene panels could not be bonded with the said adhesive.
  • Example 2 the basis of polyisocyanate/castor oil.
  • the lacquer could not be peeled off when the surface was scratched.
  • Example 3 2 mm. thick sheets (5 x 2.5 cm.) of polyoxymethylene were bent to an extent such that both ends could be inserted in a U-shaped profile 1.3 cm. wide. The bent sheets were treated as described in Examples 1
  • Process for improving the property of being bonded and lacquered of surfaces of shaped articles of polyacetals which comprises contacting the dry surface for a period of time ranging from seconds to minutes at to C. with dry pulverulent camphor-sulfonic acid.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Description

United States Patent of Germany No Drawing. Filed Oct. 20, 1964, Ser. No. 405,234
Claims priority, application Germany, Oct. 25, 1963, F 41,084 3 Claims. (Cl. 156-2) It is :known :to use high molecular weight polyacetals as thermoplasts for the manufacture of shaped articles, such as tubes, profiles and injection moulded material. Owing to the good resistance to chemicals of polyacetals, however, the shaped articles cannot be bonded or lacquered with satisfactory strength. Therefore, various methods have been proposed to treat the surfaces of shaped articles of polyacetals.
Experiments to roughen the surface mechanically with the aid of grinding cloth and analogous grinding agents, or to subject the shaped articles to an electronic pretreatment under reduced pressure, or to treat the surface with an oxidizing flame did not result in a suflicient improvement of the bonding strength of adhesives and lacquers.
Better results are obtained when the shaped articles are immersed in a solution containing an oxidizing acid. It is known, for example, to roughen the surface of shaped articles of polyoxymethylene by dipping them for minutes into a solution of about 20 C, of 11 grams of potassium bichromate in 400 parts of sulfuric acid of 95-98% strength and 14 parts of water so that it can be well wetted with water and thus bonded and lacquered. However, the process has considerable drawbacks in that it can only be applied when the area of the shaped article to be treated is free from frozen in or forced stresses (latent stress) since otherwise it breaks under the action of the acid. Shaped articles can be produced very seldom without stress and it is, therefore, necessary to subject the shaped articles to a heat treatment before treating them with the oxidizing acid. Moreover, it is rather difficult to treat limited areas of the surface.
According to another proposal shaped articles which are under stress can be treated with a mixture containing p-toluene-sulfonic acid. For this purpose the shaped article is dipped for 10-30 seconds into an agitated mixture of 75120 C. consisting of 0.3% by weight of ptoluene-sulfonic acid, 96.2% by weight of perchloroethylene, 3.0% by weight of dioxane and 0.5% by weight of kieselguhr, then placed for 1 minute in a furnace having a temperature of 120 C., rinced with water and dried in the air. After said treatment the surface of the articles can be bonded and lacquered. However, it is not uniformly roughened because the amount of p-toluenesulfonic acid adhering to the surface after dipping is non-uniformly distributed on the said surface in spite of the addition of kieselguhr, especially when articles of complicated shape are concerned. With this process, too, it is difiicult to limit the pretreatment to definite areas of the surface.
The present invention provides a process for improving the property of being bonded and lacquered of surfaces of shaped articles of polyacetals which comprises contacting the dry surface for a period of time ranging from 15 seconds to 30 minutes at 70150 C. with dry pulverulent camphor-sulfonic acid. After the removal of the loosely adhering acid, for example by blowing it off with air, the surface of the shaped article of polyacetal has a uniformly mat appearance, it can be wetted with water Patented June 7, 1966 and has a good bonding strength for adhesives and lacquers. It is especially advantageous that according to the process of the invention shaped articles with strong latent stress can be treated without heat treatment or other pretreatment. Moreover, parts of the surface can be covered and thus readily protected against the action of the acid. Panels, for example can be treated on one side only or parts can be protected by covering them with adhesive foils.
In special cases, for example when larger amounts of shaped articles are to be treated in continuous manner, it may be of advantage to treat them with dry pulverulent camphor-sulfonic acid fluidized with a hot carrier gas, for example hot air.
Owing to the fact that camphor-sulfonic acid does practically not decompose at high temperatures, it can repeatedly be used for the surface treatment of shaped articles of polyacetals. It is possible to effect a dry treatment of the surfaces of plastics also with p-toluenesulfonic acid. However, it is disadvantageous that. the latter acid decomposes during the first use and must be washed off with water.
According to the process of the invention any kind of shaped articles of polyacetals can be treated. By polyacetals there are to be understood homopolymers of formaldehyde or trioxane and the copolymers thereof with cyclic ethers of the formula in which R andR stand for hydrogen or low molecular weight alkyl radicals, or low molecular weight, halogensubstituted alkyl radicals, and R represents a methylene, an oxymethylene, or a low molecular weight alkylor halogen-a1kyl-substituted methylene or a low molecular weight alkylor halogen-alkyl-substituted oxymethylene radical and n is one of the numbers 0,' 1, 2, and 3. Especially suitable are polyacetals such as polyoxy-methylenes the terminal groups of which may have been esterified or etherified.
The following examples serve-to illustrate the invention but they are not intended to limit it thereto.
Example 1 Pulverulent camphor-sulfonic acid was spread on panels of polyoxymethylene by means of a fine-meshed sieve in a manner such that the surface was uniformly covered. The covered panels were then heated for 3 minutes at 120 C. After having removed the powder and washed otf the adhering traces of acid with water, the panels dried in air had a mat surface. They could be bonded with one another and with panels of wood, iron and other plastic materials by means of polyisocyanate/polyester adhesive. The adhesive joints had a tensile shear strength of kp./cm., whereas untreated polyoxymethylene panels could not be bonded with the said adhesive.
Example 2 the basis of polyisocyanate/castor oil. The lacquer could not be peeled off when the surface was scratched.
Example 3 2 mm. thick sheets (5 x 2.5 cm.) of polyoxymethylene were bent to an extent such that both ends could be inserted in a U-shaped profile 1.3 cm. wide. The bent sheets were treated as described in Examples 1| and 2 Without stress crazing being observed. A pretreatment of the bent sheets with sulfuric acid bichromate solution was not possible because in contact with the acid stress crazing occurred at once.
We claim:
1. Process for improving the property of being bonded and lacquered of surfaces of shaped articles of polyacetals, which comprises contacting the dry surface for a period of time ranging from seconds to minutes at to C. with dry pulverulent camphor-sulfonic acid.
2. The process of claim 1, which comprises treating the shaped articles by dipping them in dry camphor-sulfonic acid fluidized with a hot carrier gas.
3. The process of claim 1, which comprises treating shaped articles containing high molecular weight polyoxymethylene.
References Cited by the Examiner UNITED STATES PATENTS 3,069,287 12/ 1962 Hudson 11747 OTHER REFERENCES Bruner et al.: Modern Plastics, December 1961, pp. 97, 98, 101, 106, 185, and 192 relied on.
WILLIAM D. MARTIN, Primary Examiner.
M. KATZ, Assistant Examiner.

Claims (1)

1. PROCESS FOR IMPROVING THE PROPERTY OF BEING BONDED AND LACQUERED OF SURFACES OF SHAPED ARTICLES OF POLYACETALS, WHICH COMPRISES CONTACTING THE DRY SURFACE FOR A PERIOD OF TIME RANGING FROM 15 SECONDS TO 30 MINUTES AT 70 TO 150*C. WITH DRY PULVERULENT CAMPHOR-SULFONIC ACID.
US405234A 1963-10-25 1964-10-20 Process of treating surfaces of shaped articles of polyacetals with camphorsulfonic acid Expired - Lifetime US3255060A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF41084A DE1220129B (en) 1963-10-25 1963-10-25 Process for the surface treatment of polyacetal moldings

Publications (1)

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US3255060A true US3255060A (en) 1966-06-07

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BE (1) BE654837A (en)
DE (1) DE1220129B (en)
GB (1) GB1080060A (en)
NL (1) NL6412354A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419410A (en) * 1967-06-05 1968-12-31 Schjeldahl Co G T Method for treating polyester film
US3434588A (en) * 1965-09-01 1969-03-25 Scm Corp Plastic containers for paint
US3483048A (en) * 1964-12-12 1969-12-09 Hoechst Ag Process for preparing blocks of plastics material
EP0083084A2 (en) * 1981-12-29 1983-07-06 Hoechst Aktiengesellschaft Polymer moulding composition containing a filler, process for its preparation and its use
US4418162A (en) * 1980-04-30 1983-11-29 Polyplastics Co., Ltd. Process for treating the surface of polyacetal resin
US4464435A (en) * 1978-10-25 1984-08-07 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same
US20130287441A1 (en) * 2012-04-27 2013-10-31 Mitsubishi Chemical Corporation Process for producing end member, process for producing photo conductor drum unit, end member, and photo conductor drum unit

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069287A (en) * 1961-02-16 1962-12-18 Mobay Chemical Corp Coating polycarbonate plastics

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069287A (en) * 1961-02-16 1962-12-18 Mobay Chemical Corp Coating polycarbonate plastics

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3483048A (en) * 1964-12-12 1969-12-09 Hoechst Ag Process for preparing blocks of plastics material
US3434588A (en) * 1965-09-01 1969-03-25 Scm Corp Plastic containers for paint
US3419410A (en) * 1967-06-05 1968-12-31 Schjeldahl Co G T Method for treating polyester film
US4464435A (en) * 1978-10-25 1984-08-07 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetal resin composition excellent in heat stability and surface processability and process for surface treating same
US4418162A (en) * 1980-04-30 1983-11-29 Polyplastics Co., Ltd. Process for treating the surface of polyacetal resin
EP0083084A2 (en) * 1981-12-29 1983-07-06 Hoechst Aktiengesellschaft Polymer moulding composition containing a filler, process for its preparation and its use
EP0083084A3 (en) * 1981-12-29 1984-01-11 Hoechst Aktiengesellschaft Polymer moulding composition containing a filler, process for its preparation and its use
US20130287441A1 (en) * 2012-04-27 2013-10-31 Mitsubishi Chemical Corporation Process for producing end member, process for producing photo conductor drum unit, end member, and photo conductor drum unit
US9092004B2 (en) * 2012-04-27 2015-07-28 Mitsubishi Chemical Corporation Process for producing end member, process for producing photo conductor drum unit, end member, and photo conductor drum unit

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Publication number Publication date
GB1080060A (en) 1967-08-23
NL6412354A (en) 1965-04-26
BE654837A (en) 1965-04-26
DE1220129B (en) 1966-06-30

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