CA2052444A1 - Non-black synthetic rubber formulations - Google Patents

Non-black synthetic rubber formulations

Info

Publication number
CA2052444A1
CA2052444A1 CA 2052444 CA2052444A CA2052444A1 CA 2052444 A1 CA2052444 A1 CA 2052444A1 CA 2052444 CA2052444 CA 2052444 CA 2052444 A CA2052444 A CA 2052444A CA 2052444 A1 CA2052444 A1 CA 2052444A1
Authority
CA
Canada
Prior art keywords
rubber
composition according
rubber composition
pph
bromobutyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2052444
Other languages
French (fr)
Inventor
John C. Collyer
John R. Clark
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Minister of National Defence of Canada
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CA 2052444 priority Critical patent/CA2052444A1/en
Priority to EP93906313A priority patent/EP0605661A1/en
Priority to PCT/CA1992/000451 priority patent/WO1993005846A1/en
Publication of CA2052444A1 publication Critical patent/CA2052444A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D5/00—Composition of materials for coverings or clothing affording protection against harmful chemical agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/283—Halogenated homo- or copolymers of iso-olefins

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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)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

ABSTRACT

The invention disclosed relates to an injection mouldable non-black bromobutyl rubber formulation which provides twenty-four hour protection from penetration by H-agent and as such is particularly suitable for use in gas masks. The novel rubber formulation comprises bromobutyl rubber and appropriate additives to improve physical properties of the resulting material.
Significantly, an alcohol phosphate is included as part of the accelerator in an amount of 0.5 to 2.1 pph of bromobutyl rubber.

Description

2 ~
This invention relates to rubber compositions, and in particular to synthetic rubber compositions for use in gas masks and other items requiring CW agent penetration resistance.
Natural rubber has been the choice of rubber chemists for gas mask facepieces since the introduction of respiratory protecting gas masks towards the end of World War I. It has many advantages over synthetic elastomers for facepiece use including comfort, high resiliency, high strength, easy processing and moulding, non-dermatitic properties and good low temperature flexibility. HowevPr as protective equipment develops and improves, the materials they are made fxom require an ever increasing performance. With the advent of new mask designs some of the properties of the material require improvement. For example, it is highly desirable to maximize the Modulus 500~ to the range of 900-1600 psi, while keeping the Permanent Set at 500~
below about 12%. With this in mind, applicant has concentrated on providiny an improved rubbar composition for ~acepiece use that would exhibit such improved properties. Various synthetia rubb~r ~ormulations were evaluated. The material studies were based upon thc knowledge that when the flnal material was cho~cn it would bs susceptible to the present commercial injection moulding operation now used in industry.
The basic property which in~luences the material selection is its impermeability to chemical warfare (CW) agents, specifically H and GB agents. The ~tandard selected for comparison was twenty-four (24) hour proteation against H-agent :' . , ' .
.. . - ~, ~ ., ::: . .

(dichlorodiethyl sulfide). This skandard is accepted by many countries.
Accordi~g to the invention, applicant has now developed a novel non-black injection mouldable synthetic rubber composition, which provides twenty-four hour protection from penetration by H-agent, comprising:
bromobutyl rubber 100.0 silica 28.0 - 31.5 fatty acid cure promoter0.5 - 1.0 silane coupling agent (S-containing) 1.9 - ~.0 reinforcing filler 5.0 - 7.5 microcrystalline wax 0.5 - 1.0 low-temperature plasticizer0 - 8.0 rubber accelerator 2.5 - 3.0 process aid 0 - 2.2 alcohol phosphate 0.5 - 2.1 metal oxide curing agent5.0 - 5.5 pigment ~ 5 2-mercaptobenzothiazyl disul~ide 0 ~ 1.0 æul~ur 0. 0.25 diethylene glycol 0 - 3 wherein all proportions are expressed in parts by weight per one hundred parts o~ bromobutyl rubber (pph).
The silica employed is a non-dusting precipitated hydrated silica - 97.2% sio2 - particle size 100~300 microns, sold under th~ trade mark Zeosil 175. A similar material sold under the , , ~ , ' 2 ~

trade mark Zeosil 125 may also be employed. The purpose o~ thi~
component is to maximize Modulus 500% and Tensile strength.
The fatty acid cure promoter ~mployed is preferably stearic acid, although other fatty acid cure promoters could al~o be employed, such as Octoate Z, a trademark ~or a mixed fatty acid cure promoter.
The silane coupling agent is one which contains sulfur, such as vinyl mercaptosilane which is bifunctional polysulphide organosilane, sold under the trade mark SI-69. This component aids the silica to achieve the required 500~ Modulus, i.e. 900-1600 psi~
while keeping the Permanent Set at 500% below about 12%.
The reinforcing filler is a treated calcined clay-anhydrous aluminum silicate treated with a silane coupling ag~nt.
This component contributes to the optimi~ation of 500% Modulus and Permanent Set at 500%. Such materials include those sold under the trade marks Burgess KE and Nucap 100.
Various ester plasticizers have been employ0d in ~o~e formulati.ons to provide good low temperature ~lexlbil~ty and a~
lmprove resilience; including dibutyl~ebacate (D~S) Kodaflex rrx~IB~ dicapryl phthalate, dioctyl phthalate ~DOP) and dioctylazelate (DOA). The first three have been found to be equally applicable.
' -.
The microcrystalline wax employed is preferably Sunproof Canadian, although Sunproof Improved has alsQ been employed.

.
, The metal oxide curing agent employed i5 zinc oxid~.
Other curing agents such as lead oxide (Pb304~ could also be employed.
Perhaps the most significant improvement in properties is achieved by the accelerator system employed. The most di~ficult problem to overcome was having raised the Modulus 500% to levels in the range of 900-1600 psi, it was found that the Permanent Set was too high. This problem was overcome by including an alcohol phosphate, which was found to lower Permanent Set at 500% to below the useful maximum of about 12%, while maintaining Modulus 500% in the range of 900-1600 psi. A suitable alcohol phosphate is sold under the trade mark Zelec NE which is a neutralized alcohol phosphate.
The rubber accelerator per se is selected from Methazate, a trade mark for zinc dimethyldithiocarbamate; Tetrone A, a trade mark for dipentamsthylene-thiuram tetrasulfide; and Robac P25, also a trade mark for dipentamethylene-thiuram tetrasulfide.
A process aid (peptizing agent) such as Strucktol ~an : acidic ~atty acid) may be used with the accelerator in amounts up to about 2.2 pph to lubricate the polymer chain and reduce power requirements of the internal mixer.
Low-temperature T2 stiffening may be improved by the inclusion of a suitable plasticizer, e.g. TP-90-B, a trade mark for di(butoxy-ethoxy-ethy1) Pormal; and diethylene glycol.
Improved adhesion to metal, e.g. a~uminum inserts in gas masks may be achieved by including in the formulations MBTS
: (2-mercaptobenzothiazyl disulfide) and sulfur.

:. ' :
.

2~2l~

An appropriate adhesive is employed to bind the rubber material to a surface. Chemlok 205-220 (See page 193 of Chemical Dictionary) has been found acceptable for bonding to metal surfaces.
The pigments are selected to give an olive-drab coloration to the resulting material. Accordingly, the pigment composition typically comprises finely divided, BIK N-231 (Black) (0.17 pph~; Yellow 2n87 or 2089 (1.83 - 2.28 pph); and Green 4099 ~1.65 - 2.61 pph).
The results shown in the specific examples which follow illustrate the improved properties of the preferred ~ormulations according to the invention.

EXAMPLE 1 ~Lot 0081 Bromobutyl X2 100.00 Stearic Acid 1.04 ZeosiI 175 31.30 SI-69 1.96 Burge s KE 5.22 Sunproof CDN 1.04 Diethylene Glycol 2.61 TP-90 B 7.83 Black N-231 0.17 Green 4099 1.83 Yellow 2087 2.35 Added on Mill:

Zinc Oxide 5.4~
Mekhazate 2.87 Alcohol Phosphate _ Q
164.17 30 Bromobutyl X2 is a trade name for a bromobutyl rubber material available from Polysar of Sarnia, Canada. The various properties ,.. . . .
;

2~2~

of this material cured for about 12 minutes at about 160~C, in the form of slabs and buttons, are provided in table 1 which follows.
TABLE

- ~ SPEC. 1 I _. . I
RHEOMETER [viscosity~ 4.6 I _ . _ . ~ _ DENSITY 1.14 I . , . .
HARDNESS oA REX 46 ¦ SHORE _ 45 + 5 42 TENSILE T.S. MIN. 1500 2173 E~. MIN. 500% 725 (DIE C) MOD ~ 500% 900-1600 1200 MOD 5% 11.5-18.5 13.8 I _ _. __ TEAR STRENGTH Die "c" MIN _ 150 187 PERMANENT SET AT 500% 10/10 12% MAX 9.6 . .
AGEING 96h/80 c OR
: T. S. ~ % -15~20 -7.9 EL. ~ % + 20 -17.2 TEAR STRENGTH ~ % - 20 MAX ~ 2 : HARDNES5 oA ~ ~ O
_ PPHMt40C/4H 10096 . _ _ _ .
STIFFNE5S T2 MAX. -25 C PASS
_ . . _ BAYSHORE RESI~IENCE 10 Physical te~t results on the compre~sion moulded tensile sheets and on the facepieces, show that all the physical propertie~
required are within the speci~ication (SPEC) as r0cited in Table 1.

1.
The action of the alcohol phosphate has held the Permanent Set % below 12. This was also enhanced by thP treated silicate reinforcing filler.
Initially, applicant started by replacing the carbon black in the bIack rubber formulations as described in our : co-pending Canadian application Serial No. 485,232 filed 26 June, -- S

.
,, ~.

2 ~
1985, with silica and a silane coupling agent in order to raise the modulus and tensile values. However, this deteriorates the Permanent Set to levels of 20 - 30%, as well as giving low ~heometer Modulus and extremely long raise before a rheometer plateau is reached.
Having established that silane is needed to raise the Modulus to the specification levels indicated in Table 1, and that highex Modulus values create higher Permanent Set, it was necessary to determine how to lower Permanent Set without affecting Modulus.
This led tQ the investigation of alcohol phosphate and treated silicate.
We were also able to bring cure injection times down to 180 secs from a previous high of 600 secs. Physicals on the faoepieces are within =pecification as of 240 secs.

~, :

., - 7 ~

2~2~

Verifying the effect of the alcohol phosphate on the Permanent Set, and also comparing various precipitated silicas and treated silicates.

(A) (B) (C) Bromobutyl X2 100.00 100.00 100.00 Stearic Acid 1.04 1.04 1.04 Zeosil. 175 31.30 31.30 **
Zeosil 125 ** ** 35.21 ; SI-69 1.96 1.96 1.96 Burgess KE 5.22 ** **
Nucap 100 ** 5.22 5.22 Sunproof CDN 1.04 1.04 1.04 Diethylene Glycol 2.61 2.61 2.61 TP 90-B 7.83 7.83 7.83 Black N-231 0.17 0.17 0.17 Green 4099 1.83 1.83 1.83 Yellow 2089 2.61 2.61 2.61 Zinc Oxide 5.48 5.48 5.48 Accelerator additions:
A1) Methazate 3.00 A2) Methazate 3.00 Alcohol Phosphate 2.00 A3) Methazate 3.00 Alcohol Phosphate Neutralized 2.00 B1) Methazate 3.00 Alcohol Phosphate 2.00 B2) Methaza~e 3.00 Alcohol Phosphate ~.00 Strucktol A-60 2.00 Cl~ Methazats 3.00 Alcohol Phosphate 2.00 : - 8 -,, , .
' ~2~

These trials indicate that once again the Modulus 500~
values are just within or on the lower limit of the specification.
It is also apparent that the alcohol phosphate is responsible for lowering the Permanent Set to values within specification, i.e. below about 12%, while maintaining the Modulus 500~ in specification, i.e. gO0 - 1600 psi.

a) Continuing investigation of the effect of Alcohol Phosphate on Permanent Set, i.e. with and without.
b) Investigating the effect of % volatiles on the physicals.
c) Comparing Bromobutyl versus Chlorobutyl.
d~ Mill mixed in Lab at 70C.
e) Methazate versus Robac P 25.

2 ~ 4 ~

(Al) ~A2) (A3) (A4 Bromobutyl X2 100.00 100.00 100.00 **
Chlorobutyl 1255 ** ** ** 10~.00 Stearic Acid 0.52 0.52 0.52 0.52 Zeosil 175 31.30 31.30 31.3031.30 SI-69 1.96 1.96 1.96 1.96 Burgess KE 5.22 5.22 5.22 5.22 Sunproof CDN 1.04 1.04 1.04 1.04 Diethylene Glycol2O61 2.61 2.61 2.61 TP-90-B 7.83 7.83 7.83 7.83 N-231 Black 0.17 0.17 0.17 0.17 Green 4099 1.83 1.83 1.83 1.83 Yellow 2089 2.61 2.61 2.61 2.61 Alcohol Phosphate Acidic ** ** 2.09 2.09 2inc Oxide 5.48 5.48 5.48 5.48 Methazate 3.00 3.00 3.00 3.00 163.57 163.57 162.66162.66 (A2) Same formulation as (Al) except that Bromobutyl X2 and Zeosil 175 was heated at 100C for 24 hours, to drive off : volatiles, and mixed immediately upon removal from oven.
A31 & A41 - Methazate 3.00 : A32 & A42 - Robac P 25 3.00 ;

Confirmation that there is improvement in Per~anent Set of 10% points when using the alcohol phosphate neutrallzed.
Robac P 25 shows an improvement 'rensile, Modulus, lower Viscosity, higher Tear - buk at a loss of 3 - 4% points in Permanent Set.
The most interesting of all, were the resul~s of khe ~30 Chlorobutyl - higher modulus and especially a gain in resilience.
However, one major disadvantage is the extremely slow cure rate.
Accordingly, bromobutyl is preferred.

.
.

.

2~2~

A study was undextaken to svaluate the adhesion problem encountered with the metal (anodized aluminum) insert in the XC4 Mask. Adhesion in the range of 40-50 lb/min. is required.
Four formulations ware evaluated, together with different acceleration systems.
Two types of adhesives wexe used:
a) Chemlok #205 primer followed by Chemlok ~234 B

b) Chemlok #250 Trials were made by compression moulding onto aluminum strips, which were only cold solvent degreased. The same procedure that was used on the inserts.

:
~, ' ' ', ., ::

2 ~

TAB~F 5 (A) (B) (C) (D) Bromobutyl X2 100.00 100.00 100.00100.00 Zeosil 175 33.94 33.94 33.94 28.00 SI-69 2.09 2.09 2.09 2.00 Burgess KE 3.92 3.92 3.92 7.50 Sunproof CDN 0.78 0.78 0.78 0.50 Stearic Acid 0.52 0.52 0.52 1.00 Diethylene Glycol2.61 2.61 ** 2.00 TP~90-B 7.83 7.83 *~ 5.00 DBS ** ** 10.44 2.50 Yellow 2087 ** ** ** 2.28 N-~31 Black 0.16 0.16 0.16 0.17 Yellow 2089 2.35 2.35 2.35 **
Green 4099 1.65 1.65 1.65 1.65 Alcohol Phosphate Acidic ** 2.0g ** 1.50 Zinc Oxide 5.48 5.48 5.48 5.00 MBTS ** ** ** 1.00 Sulphur ** ** ** 0.25 Acceleration systems:
A1, B1, C1 - M thazate 3.13 A2, B2, C2 - Methazate 3.13 Tire sulphur 0.16 C3 - Methazate 3.13 Alcohol Phosphate Acidic 2.3S
D - Tetrone ~ 2.50 Formulations A to C exhibit a lack o~ adhesion to an anodized aluminum surface using one coat o~ Chemlok ~250. A

second coat improved adhesion marginally, but still remained unsatis~actory.
Formulation D which contains MBTS and sulphur was found to adhere better to aluminum surfaces.

Claims (16)

1. A non-black injection mouldable synthetic rubber composition, which provides twenty-four hour protection from penetration by H-agent, comprising:
bromobutyl rubber 100.0 silica 28.0 - 31.5 fatty acid cure promoter 0.5 - 1.0 silane coupling agent (S-containing) 1.9 - 2.0 reinforcing filler 5.0 7.5 microcrystalline wax 0.5 - 1.0 low-temperature plasticizer 0 - 2.5 rubber accelerator 2.5 - 3.0 process aid 0 - 2.2 alcohol phosphate 0.5 - 2.1 metal oxide curing agent 5.0 - 5.5 pigment 4 - 5
2-mercaptobenzothiazyl disulfide 0 - 1.0 sulfur 0 - 0.25 diethylene glycol 0 - 3 wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).

2. A rubber composition according to Claim 1, wherein the rubber accelerator is selected from the group consisting of zinc dimethyldithiocarbamate and dipentamethylene-thiuram tetrasulfide.
3. A rubber composition according to Claim 2, wherein the low temperature plasticizer is selected from the group consisting of dibutylsebacate, dicapryl phthalate, dioctyl phthalate and dioctylazelate.
4. A rubber composition according to Claim 3, wherein the alcohol phosphate is a neutralized alcohol phosphate.
5. A rubber composition according to Claim 4, wherein the fatty acid cure promoter is stearic acid.
6. A rubber composition according to Claim 5, wherein the metal oxide curing agent is zinc oxide.
7. A rubber composition according to Claim 1, 4 or 6, including as adhesion to metal promoter about 1.0 pph of MBTS and about 0.25 pph of sulfur.
8. A rubber composition according to Claim 6, wherein the pigment consists of a mixture of finely divided pigments to provide an olive-drab coloration to the resulting material.
9. A rubber composition according to Claim 1, consisting essentially of:
Bromobutyl rubber 100.00 Stearic Acid 1.04 Silica 31.30 Bifunctional polysulfide organo silane 1.96 Anhydrous aluminum silicate treated with a silane coupling agent 5.22 Microcrystalline wax 1.04 Diethylene Glycol 2.61 Di-butoxy-ethoxy-ethyl adipate 7.83 Black N-231 0.17 Green 4099 1.83 Yellow 2087 2.35 Zinc Oxide 5.48 Zinc dimethyldithiocarbamate 2.87 Alcohol Phosphate 0.47 wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).
10. A rubber composition according to Claim 1, consisting essentially of:
Bromobutyl rubber 100.00 Stearic Acid 1.04 Silica 31.30 Bifunctional polysulfide organo silane 1.96 Anhydrous aluminum silicate treated with a silane coupling agent 5.22 Microcrystalline wax 1.04 Diethylene Glycol 2.61 Di-butoxy-ethoxy-ethyl adipate 7.83 Black N-231 0.17 Green 4099 1.83 Yellow 2087 2.35 Zinc Oxide 5.48 Zinc dimethyldithiocarbamate 3.00 Alcohol Phosphate 2.00 wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).
11. A rubber composition according to claim 10, additionally consisting essentially of in association with the zinc dimethyl-dithiocarbamate, a fatty acid peptizing agent in an amount of 2.00, wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).
12. A rubber composition according to Claim 1, consisting essentially of:
Bromobutyl rubber 100.00 Stearic Acid 0.52 Silica 31.30 Bifunctional polysulfide organo silane 1.96 Anhydrous aluminum silicate treated with a silane oupling agent 5.22 Microcrystalline wax 1.04 Diethylene Glycol 2.61 Di-butoxy-ethoxy-ethyl adipate 7.83 Black N-231 0.17 Green 4099 1.83 Yellow 2083 2.61 Zinc Oxide 5.48 Zinc dimethyldithiocarbamate 3.00 Alcohol Phosphate 2.00 wherein all proportions are expressed in parks by weight per one hundred parts of bromobutyl rubber (pph).
13. A rubber composition according to Claim 1, consisting essentially of:
Bromobutyl rubber 100.00 Stearic Acid 0.52 Silica 31.30 Bifunctional polysulfide organo silane 1.96 Anhydrous aluminum silicate treated with a silane coupling agent 5.22 Microcrystalline wax 1.04 Diethylene Glycol 2.61 Di-butoxy-ethoxy-ethyl adipate 7.83 Black N-231 0.17 Green 4099 1.83 Yellow 2083 2.61 Zinc Oxide 5.48 Dipentamethylene-thiuram tetrasulfide 3.00 Alcohol Phosphate 2.00 wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).
14. A rubber composition according to Claim 1, consisting essentially of:
Bromobutyl rubber 100.00 Stearic Acid 0.52 Silica 33.94 Bifunctional polysulfide organo silane 2.09 Anhydrous aluminum silicate treated with a silane coupling agent 3.92 Microcrystalline wax 0.78 Diethylene Glycol 2.61 Di-butoxy-ethoxy-ethyl adipate 7.83 Black N-231 0.16 Yellow 2089 2.35 Green 4099 1.65 Alcohol Phosphate 2.09 Zinc Oxide 5.48 Zinc dimethyldithiocarbamate 3.13 wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).
15. A rubber composition according to Claim 14, additionally consisting essentially of :
Sulfur 0.16 wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).
16. A rubber composition according to Claim 1, consisting essentially of:
Bromobutyl rubber 100.00 Stearic Acid 1.00 Silica 28.00 Bifunctional polysulfide organo silane 2.00 Anhydrous aluminum silicate treated with a silane coupling agent 7.50 Microcrystalline wax 0.50 Diethylene Glycol 2.00 Di-butoxy-ethoxy-ethyl adipate 5.00 Dibutyl sebacate 2.50 Yellow 2087 2.28 Black N-231 0.17 Green 4099 1.65 Alcohol Phosphate 1.50 Zinc Oxide 5.0 2-mercaptobenzothiazyl disulfide 1.00 sulfur 0.25 Dipentamethylene-thiuram tetrasulfide 2.50 wherein all proportions are expressed in parts by weight per one hundred parts of bromobutyl rubber (pph).
CA 2052444 1991-09-23 1991-09-23 Non-black synthetic rubber formulations Abandoned CA2052444A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA 2052444 CA2052444A1 (en) 1991-09-23 1991-09-23 Non-black synthetic rubber formulations
EP93906313A EP0605661A1 (en) 1991-09-23 1992-09-23 Non-black synthetic rubber formulations
PCT/CA1992/000451 WO1993005846A1 (en) 1991-09-23 1992-09-23 Non-black synthetic rubber formulations

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA 2052444 CA2052444A1 (en) 1991-09-23 1991-09-23 Non-black synthetic rubber formulations

Publications (1)

Publication Number Publication Date
CA2052444A1 true CA2052444A1 (en) 1993-03-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2052444 Abandoned CA2052444A1 (en) 1991-09-23 1991-09-23 Non-black synthetic rubber formulations

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CA (1) CA2052444A1 (en)
WO (1) WO1993005846A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721864A (en) * 2018-12-18 2019-05-07 安徽潜隆机电科技有限公司 A kind of high-performance breathing mask rubber and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK353285D0 (en) * 1985-08-02 1985-08-02 Willi Gottlieb PROTECTIVE AND / OR WASHING MATERIAL
PT85825A (en) * 1986-10-02 1988-11-30 Bata Schuhe Ag TECHNICAL FIELD OF THE INVENTION The invention relates to a process for coating fabrics for protection against fire and flame retardants and to the production of articles therefrom.
SE464568B (en) * 1989-08-29 1991-05-13 Trelleborg Ab LAMINATE WITH RESISTANCE MAGAZINE AGAINST PERMISSION OF CHEMICALS AND PROTECTIVE MANUFACTURED BY THE LAMINATE

Also Published As

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EP0605661A1 (en) 1994-07-13
WO1993005846A1 (en) 1993-04-01

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