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US4972006A Expired / Lapsed US ⏱️ 0.0 years remaining

Postcuring of unsaturated stereolithographic specimens using aqueous initiating baths

Assignee: Stamicarbon BV
•
Filing: 1988-09-08
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Granted: 1990-11-20
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Expires: 2008-09-08
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Abstract

Abstract A method of curing a three-dimensional specimen of preformed cross-linked polymeric material containing polymerizable ethylenically-unsaturated material is provided in which the specimen is immersed in water having dissolved therein an amount of a water-soluble organic free-radical polymerization catalyst effective to transfer a polymerization-initiating amount of the catalyst into the preformed cross-linked polymeric material. This specimen containing the water-soluble organic free-radical polymerization catalyst is heated to a temperature causing polymerization, and is maintained at that temperature while the cure is completed. The aqueous bath preferably contains a catalyst mixture which includes a catalyst of oxidizing character in admixture with a reducing agent, such as an amine, and is maintained at a polymerization temperature of from 60 DEG C. to 100 DEG C. so that immersion of the specimen in a single bath completes the cure.

Inventors

  • 👤 Edward J. Murphy
  • 👤 John J. Krajewski
  • 👤 Robert E. Ansel

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 11:56
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/40; B; B29; B29C; B29C64/00; B29C64/30; B29C71/00; B29C71/0009; B33; B33Y; B33Y40/00; B33Y40/20; B33Y70/00; B29C2071/0018; B29C64/10; B29C64/106; B29C64/124; B29C71/02; B33Y10/00

Claims Analysis

Total Claims: 19
Claim 1
Independent Claim 89 words
A method of curing a three-dimensional specimen of preformed cross-linked polymeric material containing within itself polymerizable ethylenically-unsaturated material therein comprising the steps of immersing said specimen in water having dissolved therein an amount of a water-soluble organic free-radical polymerization catalyst effective to transfer a polymerization-initiating amount of said catalyst into said preformed cross-linked polymeric material, subjecting said specimen containing said water-soluble organic free-radical polymerization catalyst to a temperature sufficient to cause polymerization of the ethylenically unsaturated material, and maintaining said specimen at said polymerization temperature to cure the same.
Claim 2
Independent Claim 89 words
A method of curing a three-dimensional specimen of preformed cross-linked polymeric material containing within itself polymerizable ethylenically-unsaturated material therein comprising the steps of immersing said specimen in water having dissolved therein an amount of a water-soluble organic free-radical polymerization catalyst effective to transfer a polymerization-initiating amount of said catalyst into said preformed cross-linked polymeric material, subjecting said specimen containing said water-soluble organic free-radical polymerization catalyst to a temperature sufficient to cause polymerization of the ethylenically unsaturated material, and maintaining said specimen at said polymerization temperature to cure the same.
Claim 3
Dependent Claim 22 words
A method as recited in claim 1 in which said specimen is also immersed in water having dissolved therein a reducing agent.
Claim 4
Dependent Claim 28 words
A method as recited in claim 1 in which said specimen is immersed in water having a temperature of at least about 60° C. while it is polymerized.
Claim 5
Dependent Claim 38 words
A method as recited in claim 1 in which said specimen is made by the photopolymerization of ethylenically unsaturated material a portion of which is polyethylenically unsaturated to provide a gelatinous cross-linked polymeric matrix containing ethylenically unsaturated material.
Claim 6
Dependent Claim 16 words
A method as recited in claim 4 in which said cross-linked polymeric matrix contains monoethylenic monomers.
Claim 7
Dependent Claim 46 words
A method as recited in claim 1 in which said catalyst is a mixture of a water-soluble organic free-radical polymerization catalyst of oxidizing character and a reducing agent which are present in an aqueous bath heated to a temperature causing polymerization of said ethylenically unsaturated material.
Claim 8
Dependent Claim 16 words
A method as recited in claim 6 in which said reducing agent is a water-soluble amine.
Claim 9
Dependent Claim 15 words
A method as recited in claim 7 in which said amine is an hydroxy-functional amine.
Claim 10
Dependent Claim 34 words
A method as recited in claim 6 in which said catalyst comprises a water-soluble organic free-radical peroxide polymerization catalyst and an amine, said bath being heated to a temperature of at least 60° C.
Claim 11
Dependent Claim 26 words
A method as recited in claim 9 in which said aqueous bath is maintained at a temperature in the range of 80° C. to 100° C.
Claim 12
Dependent Claim 39 words
A method as recited in claim 1 in which said specimen is immersed in an aqueous bath containing a water-soluble organic free-radical azonitrile polymerization catalyst, said bath being heated to a temperature causing polymerization of said ethylenically unsaturated material.
Claim 13
Dependent Claim 23 words
A method as recited in claim 1 in which said bath is maintained at a temperature of from 80° C. to 100° C.
Claim 14
Dependent Claim 28 words
A method as recited in claim 2 in which said specimen within said aqueous bath is subjected to ultrasonic agitation to remove liquid materials clinging to said specimen.
Claim 15
Dependent Claim 25 words
A method as recited in claim 13 in which said ultrasonic agitation is carried out in an aqueous mediuim in which polymerization does not occur.
Claim 16
Dependent Claim 22 words
A method as recited in claim 1 in which said bath contains surfactants and/or water-miscible organic solvents to aid wetting said specimen.
Claim 17
Independent Claim 111 words
A method of curing a three-dimensional specimen of preformed cross-linked polymeric material containing within itself polymerizable ethylenically-unsaturated material made by the photopolymerization of ethylenically unsaturated material at least a portion of which is polyethylenically unsaturated to provide a gelatinous cross-linked polymeric matrix containing ethylenically unsaturated material, comprising the steps of immersing said specimen in water having dissolved therein a water-soluble organic free-radical polymerization catalyst of oxdizing character and an amine, said water being heated to a temperature of at least 60° C., and holding said specimen in said heated bath to cause polymerization of said ethylenically unsaturated material to thus cure said specimen, and withdrawing the cured specimen from said bath.
Claim 18
Independent Claim 111 words
A method of curing a three-dimensional specimen of preformed cross-linked polymeric material containing within itself polymerizable ethylenically-unsaturated material made by the photopolymerization of ethylenically unsaturated material at least a portion of which is polyethylenically unsaturated to provide a gelatinous cross-linked polymeric matrix containing ethylenically unsaturated material, comprising the steps of immersing said specimen in water having dissolved therein a water-soluble organic free-radical polymerization catalyst of oxdizing character and an amine, said water being heated to a temperature of at least 60° C., and holding said specimen in said heated bath to cause polymerization of said ethylenically unsaturated material to thus cure said specimen, and withdrawing the cured specimen from said bath.
Claim 19
Dependent Claim 30 words
A method as recited in claim 16 in which said amine is an hydroxy-functional amine and said bath is maintained at a temperature of from 60° C. to 80° C.

References Cited (Backward Citations)

US3083118A Cited
US4575330A Cited
US4575330B1 Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1993-11-19 1994-05-21 1994-11-20 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1997-11-19 1998-05-21 1998-11-20 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2001-11-19 2002-05-21 2002-11-20 $7700.00 Window Closed / Lapsed

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