GB1599360A - High nitrile resins containing maleic anhydride - Google Patents

High nitrile resins containing maleic anhydride Download PDF

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Publication number
GB1599360A
GB1599360A GB25677/78A GB2567778A GB1599360A GB 1599360 A GB1599360 A GB 1599360A GB 25677/78 A GB25677/78 A GB 25677/78A GB 2567778 A GB2567778 A GB 2567778A GB 1599360 A GB1599360 A GB 1599360A
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parts
psi
weight
styrene
hours
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GB25677/78A
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Standard Oil Co
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Standard Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes

Abstract

The copolymer is derived from monomers comprising A) from 60 to 90% by weight of at least one nitrile, B) from 1 to 30% by weight of maleic anhydride and C) from 5 to 25% by weight of at least one representative of the group consisting of 1.) styrene or alpha -methylstyrene, 2.) an ester, 3.) an alpha -olefin, 4.) a vinyl ether, and 5.) vinyl acetate, where the percentages by weight of (A), (B) and (C) are based on the total weight of (A) + (B) + (C). The copolymers have excellent solvent resistance and, due to their high impact strength and low permeability to gases and vapours, are suitable for use in the packaging industry and are particularly suitable for the production of bottles, films, sheets, tubes and other types of container for liquids and solids.

Description

(54) HIGH NITRILE RESINS CONTAINING MALEIC ANHYDRIDE (71) We, THE STANDARD OIL COMPANY a corporation organised under the laws of the State of Ohio, of Midland Building, Cleveland, Ohio 44115, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to novel polymeric compositions which have high heatdistortion temperatures, good gas barrier properties and low creep characteristics.
which are composed of an olefinically unsaturated nitrile, another monovinyl component and maleic anhydride and optionally a rubbery polymer of conjugated diene monomer, and to the process for manufacture of these compositions.
The novel polymeric products of this invention are prepared by solution polymerisation in the presence of a suitable solvent and a free-radical initiator of 100 parts by weight of (A) from 60 to 90% by weight of at least one nitrile having the structure
where R is hydrogen, a lower alkyl group having from I to 4 carbon atoms, or a halogen, (B) from I to 30% by weight of maleic an hydride, and (C) from 5 to 25 ó by weight of at least one of (I) styrene or alpha-methyl styrene; (2) an ester having the structure
in which R1 represents hydrogen, an alkyl group having from I to 4 carbon atoms, or a halogen, and R2 represents an alkyl group having from 1 to 6 carbon atoms; (3) an alpha-olefin having the structure
in which R' and R" represent alkyl groups having from 1 to 7 carbon atoms, (4) methyl vinyl ether, ethyl vinyl ether, a propyl vinyl ether, or a butyl vinyl ether, or (5) vinyl acetate, wherein the weight percentages of (A), (B) and (C) are based on the combined weight of (A) plus (B) plus (C), in the presence of from 0 to 40 parts by weight of (D) a rubbery polymer of a conjugated diene monomer which is butadiene or isoprene and optionally at least one comonomer which is styrene, a nitrile monomer having the structure
in which R is as defined above or an ester having the structure
in which R1 and R2 are as defined above, said rubbery polymer containing from 0 to 50% by weight of comonomer.
The conjugated dienes useful in this invention are butadiene and isoprene, because of their ready availability and their excellent copolymerization properties.
The olefinically unsaturated nitriles useful in this invention are the alpha betaolefinically unsaturated mononitriles having the structure
in which R represents hydrogen, a lower alkyl group having from 1 to 4 carbon atoms, or a halogen. Such compounds include acrylonitrile, alphachloroacrylonitrile, alphafluoroacrylonitrile, methacrylonitrile, and ethacrylonitrile.
The most preferred olefinically unsaturated nitrile is acrylonitrile.
The other monovinyl monomer components copolymerizable with the olefinically unsaturated nitriles which are useful in this invention are one or more of the vinyl aromatic monomers, esters of olefinically unsaturated carboxylic acids, vinyl esters, vinyl ethers or alpha-olefins, or specified under component (C).
The esters of olefinically unsaturated carboxylic acids are those having the structure
in which R, represents hydrogen, an alkyl group having from 1 to 4 carbon atoms, or a halogen, and R2 is an alkyl group having from 1 to 6 carbon atoms. Compounds of this type include methyl acrylate, ethyl acrylate, the propyl acrylates, the butyl acrylates, the amyl acrylates, and the hexyl acrylates; methyl methacrylate, ethyl methacrylate, the propyl methacrylates, the butyl methacrylates, the amyl methacrylates, and the hexyl methacrylates; methyl alpha-chloroacrylate and ethyl alpha-chloroacrylate. Most preferred in the present invention are methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
The alpha-olefins useful in the present invention are those having at least 4 and as many as 10 carbon atoms and having the structure
wherein R' and R" represent alkyl groups having from 1 to 7 carbon atoms, amd more specifically preferred are alpha-olefins such as isobutylene, 2 - methyl butene - 1, 2 methyl pentene - 1, 2 - methyl hexene - 1, 2 - methyl heptene - , 2 - methyl octene 1, 2- ethyl butene - 1 and 2- propyl pentene - 1. Most preferred is isobutylene.
Meleic anhydride is an essential component of the novel compositions embodied in this invention.
The polymeric compositions of the present invention are prepared by solution polymerization in the presence of a suitable solvent and a free-radical generating polymerization initiator preferably at a temperature in the range of from about 0 to 100"C in the substantial absence of molecular oxygen.
The rubbery polymers which may be included in the resins of this invention are homopolymers of butadiene and isoprene as well as copolymers of these dienes and another monomer component which is a nitrile of the formula defined above for example acrylonitrile, styrene, an ester of the formula defined above, for example ethyl acrylate, and mixtures thereof, in which there is present at least 50 Ó by weight of the total monomers of butadene or isoprene.
The novel polymers produced by the process of this invention are readily processed thermoplastic materials which can be thermoformed into a wide variety of useful articles in any of the conventional ways employed with known thermoplastic materials, such as by extrusion, milling, molding, drawing or injecting. The polymeric products of this invention have excellent solvent resistance and their impact strength and low permeability to gases and vapours make them useful in the packaging industry, and they are particularly useful in the manufacture of bottles. film, sheet, pipes and other types of containers for liquids and solids.
In the following illustrative examples, the amounts of ingredients are expressed in parts by weight unless otherwise indicated.
Example 1 A. An acrylonitrile-styrene copolymer which is outside the scope of the present invention was prepared in a polymerization reactor to which were added 75 parts of acrylontrile, 3 parts of styrene and 75 parts of methyl ethyl ketone. The mixture was stirred and brought to 76"C under an atmosphere of nitrogen. A feed of 22 parts of styrene, 25 parts of methyl ethyl ketone and 0.3 part of azobisisobutryonitrile was added continuously and uniformly over a 4.5-hour period. The final reaction mixture was maintained at 76-780C for an additional hour. The overall conversion of monomers to polymer was 68% of theory.
The contents of the reactor were poured into a stirred mixture of 1:1 by volume benzene:petroleum ether. The solid polymer was isolated and dried at reduced pressure and 45--60"C for 48 hours. This resin was found to have an ASTM heatdistortion temperature of 84--94"C, a flexural strength of 17.1x103 psi, a flexural modulus of 5.50xl05 psi, a tensile strength of 14.1 x 103 psi, an oxygen transmission rate of 3.5 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 8.0 gmmil/100 inches2/24 hours/atmosphere.
B. An acrylonitrile - styrene - maleic anhydride terpolymer which is within the scope of the present invention was prepared by the procedure of A of this Example except that the continuous feed was made up of 5 parts of maleic anhydride, 17 parts of styrene. 25 parts of methyl ethyl ketone and 0.3 parts of azobisisobutyronitrile and the continuous feed was added uniformly over a 5-hour period. The overall conversion of monomers to polymer was 80% of theory.
The resin thus produced was found to have an ASTM heat-distortion temperature of 102"C, a flexural strength of 18.7xl03 psi, a flexural modulus of 6.06x105 psi, a tensile strength of 15.2x 103 psi, an oxygen transmission rate of 4.6 ccmil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 0.9 gm-mil/100 inches2/24 hours/atmosphere.
Example 2 The precedure of Example IA was followed except that the initial reactor charge was 70 parts of acrylonitrile, 2.8 parts of styrene, 75 parts of methyl ethyl ketone and the continuous feed was made up of 5 parts of maleic anhydride, 22.2 parts of styrene. 25 parts of methyl ethyl ketone and 0.3 part of azobisisobutyronitrile. The continuous feed was added uniformly over a 6-hour period. The overall conversion of monomers to polymer was 81 ó of theory.
The resulting resinous polymer was found to have an ASTM heat-distortion temperature of 104"C, a flexural strength of 18.9x 103 psi, a flexural modulus of 6.13x105 psi and a tensile strength of 14.2x103 psi.
Example 3 A polymer was prepared by the procedure described in Example 2 using an initial reactor charge of 70 parts of acrylonitrile, 2.8 parts of styrene and 75 parts of methyl ethyl ketone and a continuous feed made up of 10 parts of maleic anhydride, 17.8 parts of styrene, 25 parts of methyl ethyl ketone and 0.3 part of azobisisobutyronitrile. The resulting resin was found to have an ASTM heat-distortion temperature of 107"C, a flexural modulus of 6.03x 105 psi, an oxygen transmission rate of 2.7 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 5.4 gm-mil/100 inches2/24 hours/atmosphere.
Example 4 A. A copolymer of acrylonitrile and methyl acrylate which is outside the scope of this invention was prepared by adding to a polymerization reactor 75 parts of acrylonitrile, 25 parts of methyl acrylate, 100 parts of methyl ethyl ketone and 0.1 part of azobisisobutyronitrile. The polymerization reaction was carried out for 2 hours at 770C with stirring under a nitrogen atmosphere. The polymer was isolated by coagulation with a 1:1 by volume mixture of benzene:petroleum ether. The dried resinous polymer was found to have an ASTM heat-distortion temperature of 76"C, a flexural strength of 21.4x103 psi, a flexural modulus of -6.56x105 psi, a tensile strength of 10.6x103 psi, ~ an oxygen transmission rate of 0.35 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 4.3 gm-mil/100 inches2/24 hours/atmosphere.
B. The procedure of A of this Example was followed except that the ingredients of the polymerization mixture were 70 parts of acrylonitrile, 20 parts of methyl acrylate, 10 parts of maleic anhydride, 100 parts of methyl ethyl ketone and 0.1 part of azobisisobutyronitrile. The resulting polymer was found to have an ASTM heatdistortion temperature of 83"C, a flexural strength of 25.5x 103 psi, a flexural modulus of 0.75x105 psi, a tensile strength of 13.4x103 psi. an oxygen transmission rate of 0.24 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 3.2 gm-mil/100 inches2/24 hours/atmosphere.
Example 5 The procedure of Example 4A was repeated except that the ingredients of the polymerization mixture were 60 parts of acrylonitrile, 20 parts of methyl acrylate, 20 parts of maleic anhydride, 100 parts of methyl ethyl ketone and 0.1 part of azobisisobutyronitrile. The resulting polymer was found to have an ASTM heatdistortion temperature of 79"C, a flexural strength of 21.7x 103 psi, a flexural modulus of 6.49x105 psi and a tensile strength of 16.2x103 psi.
WHAT WE CLAIM IS: 1. The polymeric composition resulting from the solution polymerisation in the presence of a suitable solvent and a free radical initiator of 100 parts by weight of
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (13)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    additional hour. The overall conversion of monomers to polymer was 68% of theory.
    The contents of the reactor were poured into a stirred mixture of 1:1 by volume benzene:petroleum ether. The solid polymer was isolated and dried at reduced pressure and 45--60"C for 48 hours. This resin was found to have an ASTM heatdistortion temperature of 84--94"C, a flexural strength of 17.1x103 psi, a flexural modulus of 5.50xl05 psi, a tensile strength of 14.1 x 103 psi, an oxygen transmission rate of 3.5 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 8.0 gmmil/100 inches2/24 hours/atmosphere.
    B. An acrylonitrile - styrene - maleic anhydride terpolymer which is within the scope of the present invention was prepared by the procedure of A of this Example except that the continuous feed was made up of 5 parts of maleic anhydride, 17 parts of styrene. 25 parts of methyl ethyl ketone and 0.3 parts of azobisisobutyronitrile and the continuous feed was added uniformly over a 5-hour period. The overall conversion of monomers to polymer was 80% of theory.
    The resin thus produced was found to have an ASTM heat-distortion temperature of 102"C, a flexural strength of 18.7xl03 psi, a flexural modulus of 6.06x105 psi, a tensile strength of 15.2x 103 psi, an oxygen transmission rate of 4.6 ccmil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 0.9 gm-mil/100 inches2/24 hours/atmosphere.
    Example 2 The precedure of Example IA was followed except that the initial reactor charge was 70 parts of acrylonitrile, 2.8 parts of styrene, 75 parts of methyl ethyl ketone and the continuous feed was made up of 5 parts of maleic anhydride, 22.2 parts of styrene. 25 parts of methyl ethyl ketone and 0.3 part of azobisisobutyronitrile. The continuous feed was added uniformly over a 6-hour period. The overall conversion of monomers to polymer was 81 ó of theory.
    The resulting resinous polymer was found to have an ASTM heat-distortion temperature of 104"C, a flexural strength of 18.9x 103 psi, a flexural modulus of 6.13x105 psi and a tensile strength of 14.2x103 psi.
    Example 3 A polymer was prepared by the procedure described in Example 2 using an initial reactor charge of 70 parts of acrylonitrile, 2.8 parts of styrene and 75 parts of methyl ethyl ketone and a continuous feed made up of 10 parts of maleic anhydride, 17.8 parts of styrene, 25 parts of methyl ethyl ketone and 0.3 part of azobisisobutyronitrile. The resulting resin was found to have an ASTM heat-distortion temperature of 107"C, a flexural modulus of 6.03x 105 psi, an oxygen transmission rate of 2.7 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 5.4 gm-mil/100 inches2/24 hours/atmosphere.
    Example 4 A. A copolymer of acrylonitrile and methyl acrylate which is outside the scope of this invention was prepared by adding to a polymerization reactor 75 parts of acrylonitrile, 25 parts of methyl acrylate,
    100 parts of methyl ethyl ketone and 0.1 part of azobisisobutyronitrile. The polymerization reaction was carried out for 2 hours at 770C with stirring under a nitrogen atmosphere. The polymer was isolated by coagulation with a 1:1 by volume mixture of benzene:petroleum ether. The dried resinous polymer was found to have an ASTM heat-distortion temperature of 76"C, a flexural strength of 21.4x103 psi, a flexural modulus of -6.56x105 psi, a tensile strength of 10.6x103 psi, ~ an oxygen transmission rate of 0.35 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 4.3 gm-mil/100 inches2/24 hours/atmosphere.
    B. The procedure of A of this Example was followed except that the ingredients of the polymerization mixture were 70 parts of acrylonitrile, 20 parts of methyl acrylate, 10 parts of maleic anhydride, 100 parts of methyl ethyl ketone and 0.1 part of azobisisobutyronitrile. The resulting polymer was found to have an ASTM heatdistortion temperature of 83"C, a flexural strength of 25.5x 103 psi, a flexural modulus of 0.75x105 psi, a tensile strength of 13.4x103 psi. an oxygen transmission rate of 0.24 cc-mil/100 inches2/24 hours/atmosphere and a water vapor transmission rate of 3.2 gm-mil/100 inches2/24 hours/atmosphere.
    Example 5 The procedure of Example 4A was repeated except that the ingredients of the polymerization mixture were 60 parts of acrylonitrile, 20 parts of methyl acrylate, 20 parts of maleic anhydride, 100 parts of methyl ethyl ketone and 0.1 part of azobisisobutyronitrile. The resulting polymer was found to have an ASTM heatdistortion temperature of 79"C, a flexural strength of 21.7x 103 psi, a flexural modulus of 6.49x105 psi and a tensile strength of 16.2x103 psi.
    WHAT WE CLAIM IS: 1. The polymeric composition resulting from the solution polymerisation in the presence of a suitable solvent and a free radical initiator of 100 parts by weight of
    (A) from 60 to 90% by weight of at least one nitrile having the structure
    wherein R is hydrogen, a lower alkyl group having from 1 to 4 carbon atoms, or a halogen, (B) from 1 to 30% by weight of maleic anhydride, and (C) from 5 to 25% by weight of at least one of (1) styrene or alpha-methyl styrene; (2) an ester having the structure
    in which R1 represents hydrogen, an alkyl group having from I to 4 carbon atoms, or a halogen, and R2 represents an alkyl group having from I to 6 carbon atoms, (3) an alpha-olefin having the structure
    in which R' and Rt represent alkyl groups having from 1 to 7 carbon atoms, (4) methyl vinyl ether, ethyl vinyl ether, a propyl vinyl ether or a butyl vinyl ether or (5) vinyl acetate, wherein the weight percentages of (A), (B) and (C) are based on the combined weight of (A) plus (B) plus (C), in the presence of from 0 to 40 parts by weight of (D) a rubbery polymer of a conjugated diene monomer which is butadiene or isoprene and optionally at least one comonomer which is styrene, a nitrile monomer having the structure
    in which R is as defined above, or an ester having the structure
    in which R1 and R2 are as defined above, said rubbery polymer containing from 0 to 50 Ó by weight of comonomer.
  2. 2. A composition as claimed in claim 1 in which (A) is acrylonitrile.
  3. 3. A composition as claimed in claim 1 or claim 2 in which (C) is styrene.
  4. 4. A composition as claimed in claim 1 or claim 2 in which (C) is methyl acrylate.
  5. 5. A composition as claimed in any of claims 1 to 4 in which (D) is a butadiene acrylonitrile copolymer.
  6. 6. The process comprising polymerizing in a solvent in the presence of a free-radical initiator 100 parts by weight of (A) from 60 to 90% by weight of at least one nitrile having the structure
    in which R represents hydrogen, a lower alkyl group having from 1 to 4 carbon atoms, or a halogen, (B) from 1 to 30% by weight of maleic anhydride, and (C) from 5 to 25% by weight of at least one of (1) styrene or alpha-methyl styrene; (2) an ester having the structure
    in which R1 represents hydrogen, an alkyl group having from 1 to 4 carbon atoms, or a halogen, and R2 represents an alkyl group having from I to 6 carbon atoms, (3) an alpha-olefin having the structure
    in which R' and R" represent alkyl groups having from I to 7 carbon atoms, (4) methyl vinyl ether, ethyl vinyl ether, a propyl vinyl ether, or a butyl vinyl ether, and (5) vinyl acetate, wherein the weight percentages of (A), (B) and (C) are based on the combined weight of (A) plus (B) plus (C), in the presence of from 0 to 40 parts by weight of (D) a rubbery polymer of a conjugated diene monomer which is butadiene or isoprene and optionally at least one comonomer which is styrene, a nitrile monomer having the structure
    in which R is as defined above, and an ester having the structure
    in which R, and R2 are as defined above, said rubber polymer containing from 0 to 50% by weight of comonomer.
  7. 7. A process as claimed in claim 6 in which (A) is acrylonitrile.
  8. 8. A process as claimed in claim 6 or claim 7 in which (C) is styrene.
  9. 9. A process as claimed in claim 6 or claim 7 in which (C) is methyl acrylate.
  10. 10. A process as claimed in any of claims 6 to 9 in which (D) is a butadiene acrylonitrile copolymer.
  11. 11. A process as claimed in Claim 6, substantially as herein described with reference to any of the Examples.
  12. 12. A composition as claimed in Claim 1, substantially as herein described with reference to any of the Examples.
  13. 13. A composition as claimed in any of Claims 1 to 5 or Claim 12, when prepared by a process as claimed in any of Claims 6 to Il.
GB25677/78A 1977-06-15 1978-05-31 High nitrile resins containing maleic anhydride Expired GB1599360A (en)

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JP (1) JPS546091A (en)
AT (1) AT366708B (en)
AU (1) AU518735B2 (en)
BE (1) BE868108A (en)
CA (1) CA1106536A (en)
CH (1) CH637661A5 (en)
DE (1) DE2824713A1 (en)
DK (1) DK155608C (en)
FR (1) FR2394577B1 (en)
GB (1) GB1599360A (en)
IT (1) IT1096376B (en)
NL (1) NL7806484A (en)
SE (1) SE443364B (en)
ZA (1) ZA782898B (en)

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DE2747822C2 (en) * 1977-10-26 1985-05-30 Bayer Ag, 5090 Leverkusen Thermoplastic molding compounds
JP4746684B2 (en) * 2009-03-24 2011-08-10 有限会社長州電気 Telescopic device

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US2734888A (en) * 1951-08-31 1956-02-14 Projducts
DE919140C (en) * 1951-12-05 1954-10-14 Roehm & Haas G M B H Process for improving the properties of acrylonitrile copolymers
JPS4920294A (en) * 1972-06-16 1974-02-22
US3998907A (en) * 1972-08-29 1976-12-21 Arco Polymers, Inc. Rubber-modified dicarboxylic acid imide copolymers
IT1043117B (en) * 1975-10-03 1980-02-20 Snam Progetti SHOCK RESINS AND METHOD FOR THEIR AREPARATION
ZA869120B (en) * 1985-12-04 1987-10-28 Max Planck Gesellschaft New phosphorus compounds and medicaments containing them

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ATA393378A (en) 1981-09-15
DK269978A (en) 1978-12-16
IT7824274A0 (en) 1978-06-06
SE443364B (en) 1986-02-24
FR2394577B1 (en) 1985-11-15
SE7806875L (en) 1978-12-16
ZA782898B (en) 1979-05-30
DK155608B (en) 1989-04-24
DK155608C (en) 1989-10-16
AU518735B2 (en) 1981-10-15
BE868108A (en) 1978-10-02
AU3632378A (en) 1979-11-29
JPS546091A (en) 1979-01-17
JPS6315286B2 (en) 1988-04-04
FR2394577A1 (en) 1979-01-12
DE2824713A1 (en) 1979-01-04
IT1096376B (en) 1985-08-26
CA1106536A (en) 1981-08-04
AT366708B (en) 1982-05-10
CH637661A5 (en) 1983-08-15
NL7806484A (en) 1978-12-19

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PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19920531