CA1237224A - Heat resistant resin composition - Google Patents
Heat resistant resin compositionInfo
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- CA1237224A CA1237224A CA000442902A CA442902A CA1237224A CA 1237224 A CA1237224 A CA 1237224A CA 000442902 A CA000442902 A CA 000442902A CA 442902 A CA442902 A CA 442902A CA 1237224 A CA1237224 A CA 1237224A
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- monomer
- monomer residue
- aromatic
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Abstract
ABSTRACT:
A heat resistant resin composition comprising from 10 to 90% by weight of a copolymer A and from 90 to 10% by weight of a copolymer B, in which the copolymer A is composed of an N-aromatic maleimide monomer residue, a maleimide monomer residue, a vinyl aromatic monomer residue and, optionally other vinyl monomer residue, the total content of the N-aromatic maleimide monomer residue and the maleimide monomer residue being from 10 to 45%, the content of the N-aromatic maleimide monomer residue being greater than the content of the maleimide monomer residue, the content of the vinyl aromatic monomer residue being from 90 to 55% and the content of said other vinyl monomer residue being from 0 to 20%, and the copolymer B is composed of a vinyl cyanide monomer residue, a vinyl aromatic monomer residue and, optionally other vinyl monomer residue, the content of the vinyl cyanide monomer residue being from 20 to 55%, the content of the vinyl aromatic monomer residue being from 80 to 45% and the content of said other vinyl monomer residue being from 0 to 20%.
A heat resistant resin composition comprising from 10 to 90% by weight of a copolymer A and from 90 to 10% by weight of a copolymer B, in which the copolymer A is composed of an N-aromatic maleimide monomer residue, a maleimide monomer residue, a vinyl aromatic monomer residue and, optionally other vinyl monomer residue, the total content of the N-aromatic maleimide monomer residue and the maleimide monomer residue being from 10 to 45%, the content of the N-aromatic maleimide monomer residue being greater than the content of the maleimide monomer residue, the content of the vinyl aromatic monomer residue being from 90 to 55% and the content of said other vinyl monomer residue being from 0 to 20%, and the copolymer B is composed of a vinyl cyanide monomer residue, a vinyl aromatic monomer residue and, optionally other vinyl monomer residue, the content of the vinyl cyanide monomer residue being from 20 to 55%, the content of the vinyl aromatic monomer residue being from 80 to 45% and the content of said other vinyl monomer residue being from 0 to 20%.
Description
Our Ref .: MST - 6C
~Z3~
IIF,AT RESISTANT RESIN COl~qPOSlTlON
Tl~e pres~nt irl~ntiorl relates to a heat resistallt rcsin composition havillg a high thermal deformation temperature and a hig]l thermal decomposition temperature.
A copo]ymer (SMA) of a vinyl aromatic monomer with maleic 5 anhydride has a high theImal deformation temperature and good compatibi]ity wit]l other thermoplclstic resins such as a styrene-acrylollitrile copolyrner (AS resin), and it is useful for the preparation of a heat resistant resin cornposition.
However, S~1A is infeLior in its stability at a high temper~ture, l0 and it has drawbacks that when heated at a temperature of 230C or il;g]ler, it tends to lead to foaming or weight reduction and it is likely to undergo cross-linking, w]lereby the molding processability of the resin composition contaillillg Sl\~A is considerably impaired. It has been attempted to improve the high temperature stability of SMA by 15 incorpoI ating various additives such as anti-oxidants, but no satis-factory results have been obtained. The present inve]ltors have condllcted extensive rescarches with an aim to overcome the above-mel1tiollcd drawbacks and to present A heat resistault resin composition containing a copolymer composed of a vinyl aromatic monomer and a 20 maleic acid derivative and havillg a high temperature stability and a high thel mal dcformation temperature. As a result, the present ~7;~24 invention has been accolllp]ished.
Namely, the above~mcl-tioned object of the present invention hns bcell attnined by a heat resistallt r esin composition comprising fZom 10 to 90% by ~veight of a copolymer A and from 90 to 10~ by wcight of a copolymer B, in ~V]liC]I the copolymer A is composed of an N-arofnatic mal~imide monolller rcsi(lue, a mn]cimide monomer rcsidue, a vinyl aromatic mo7l0lller residue nnd, optionally other vinyl monomer residue, t]le total ~or~tent of the N - aromntic maleimide monomer residue and the malciinide monomer r esidue bcing from 10 to 45%, the content of the N-aromatic m~lcimide monomer residue being grcater than the content of the maleimide monomer residue, the content of the vinyl aromatic monomcr residue being from 90 to 55% and the content - of s~lid other vinyl monomer residue being from 0 to 20%, and the copolymer B is composed of a vinyl cyanide monolller residue, a vinyl aromatic monomer rcsidue and, optionally other vinyl monomer residue, the content of the vinyl cyanide monomer residue being from 20 to 55%, the content of v-inyl aromatic mollolner residue bcing from 80 to 45% and the content of said other vinyl monomer residue beïng from 0 to 20o.
In the prcscllt invclltion, the content of each monolller residlle is represented by a proportion by percentage of the number of units of the monomer residue to the total number of units of val~ious monomer r esidues contailled in the copoiymer conccrned.
- 3- ~2~722~
Now, the present invention will be described in detail with reference to the preferred embodiments.
As the villyl aromatic compound to be used in the present invention, styrene is most common, but other compounds such as 5 ~-methylstyrene, p-methylstyrene, t-butylstyrene, a styrene halogenide or a mixture thereof may be used. As the vinyl cyanide compound, acrylonitrile, Methacrylonitrile or a mixture thereof is usually used.
The N-aromatic maleimide may be obtained by condensing a primary aromatic amine with fumaric acid, maleic acid, maleic acid 10 anhydride or other maleic acid derivatives. As the p1imary aromatic amine, aniline or an aniline derivative with its benzene ring substituted by an alkyl group, a halogen atom or a nitro group, such as toluidine or nitroaniline is used. Further, phenylenediamine or c~-naphthylarnine may also be used. These amines may be used alone or in combination 15 as a mixture of two or more different kinds. The maleimide may be obtained by condensing a maleic acid derivative such as maleic acid anhydlide, ~vith ammonia. The copolymer A may be produced by copolymelizing an N-aromatic maleimide with other monomers. Ilowever, as will be mentioned hereinafter, it is preferred to employ a method 20 wherein a maleic acid anhydride copolymer is reacted witll the above-mentioned amine and ammonia during the polymerization step or in a separate step to convert it into an imide, since this method is simple and the required monomers are readily available.
The content of the N-aromatic maleimide in the copolymer A
25 must be greater than the content of the maleimide. Otherwise, the compatibility of the copolymer A with the copolymer B will be poor, thus leading to an infcrior physical properties of the resin composition thereby obtained. ~Vithin the above-mentioned r~lge, the greater _ 4_ ~2~7~24 the content of the maleimide residue is, the higher the thermal deformation temperature becomes.
The total content of the N-aromatic maleimide residue and the maleimide residue contained in the copolymer A should be from 10 to 5 45%. If the total amount exceeds 45%, the flo~vability tends to decrease and the mo]ding opcration becomes difficult. On the other hand, if tlle total amount is less than 10%, no adequate improvement of the thermal deformalion temperature is obtainable.
Further, the content of the vinyl aromatic monomer residue should 10 be from 90 to 55%. If the content of the vinyl aromatic monomer residue increases, the flowability will be improved, but the thermal deformation temperature decreases.
A part of the vinyl aromatic monomer residue may be replaced by other monomer, for instance, a vinyl cyanide monomer such as 15 acrylonitrile or methacrylonitrile, an ester of acrylic acid or metha-acrylic acid such as methylacrylate or methylmethacrylate, or a derivative of maleic acid or fumaric acid such as maleic anhydlide, dimethyl maleataor dimethyl fumarate, as the case requires. In such a case, the content of the other monomer for replacemellt should be 20 at most 20%. If the content exceeds 20%, the compatibility with other styrene-type resin is likely to be inferior.
- Adequate compatibility with the copolymer A will be obtained if the content of the vinyl cyanide monomer residue in the copolymer B
is within a ran~e of from 20 to 55%, the rest being the vinyl aromatic 25 monomer residue, A part of the ~,inyl aromatic monomer residue may preferably be substituted by other vinyl monomer such as an ester of acrylic acid or methacrylic acid, as the case requires. In such a case, the _ 5- ~Z~7~2~
content of said other vinyl monomer residue sllould preferably be at most 20%, whel-eby no adverse effects will be imparted to the compatibility with other resins.
The composition according to the present invention is superior 5 in the heat resistance, high temperature stability, solvent resistance and ~lowabilitv during the molding operation. Further, the composi-tion of the present invention has good compatibility with an ABS resin, a MBS resin, an AES resin, an ACS resin or an AAS resin, and accord-ingly it is possib]e to improve the shock resistance by incorporating such 10 resins. In such a case, it is readily possible to bling the thermal deform-ation temperature (a Vicat softening point) to at least 115C. Further, a reinforcing material or fiiler such as g]ass fiber, carbon fiber, ta]c or calcium carbonate, or other additives may be incoporated.
Now, the process of the present invention will be described.
15 Firstly, bulk polymerization is conducted whi]e continuously supplying maleic acid anhydride in the presence of the vinyl aromatic monomer.
The amount of the maleic acid anhydride monomer to be added here is preferably rom 10 to 45 molar %. The polymelization temperature is preferably from 90 to 130C, and no polymerization initiator may be 20 required. The conversion in this step is at ]east 10% by ~veight and can be increased as far as the stirring driving i`orce of the polymerization apparatus permits. The polymelization time is determilled depending upon the conversion, the polymerization temperature, the concentration of the maleic acid anhydlide, and is usually within 25 a range of from 1 to 10 hours. After completion of the continuous supply o~ tlle maleic acid anllydlide, the maleic acid anllydIide in the monomer mixture will rapidly be consumed, ~vhereupon the system becomes in the form of a syrup composed substantially of the copolymer - 6- ~Z~7~2~
and the vinyl aromatic monomer. A part of the vinyl aromatic compound to be initially present rnay be replaced by an ester of acrylic acid, an ester of methacrylic acid or a vinyl cyanide compound.
To this syrup, a vinyl cyanide monomer is added and uniformly 5 mixed. The amount of the addition is adjusted to bring the content of the vinyl c:yan;de monolller residue in tlle copolymer formed by the reaction with the remaining vinyl aromatic compound to a level of from 20 to 55%.
This syrup is suspended in water, alld the vinyl aromatic monomer 10 and the vinyl cyanide monomer are co-polymerized by suspension polymerization. A conventional polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide may be used. Likewise, the suspension agent may be a conventional one such as polyvinyl alcohol, polyacrylamide or barium sulfate. The polymerization temper-15 ature is usually within a range of from 60 to 160C, and thepolymerization time is determined depending upon the polymerization temperature and the type and amount of the initiator, but, is usually within a range of from 1 to 10 houls. In order to maintain the content of the vinyl cyanide monomer residue in the resulting copolymer to be 20 constant, the vinyl aromatic monomer or the vinyl cyanide rnonomer may be added continuously or intermittently. Further, in order to reduce tlle amount of the resulting copolyrner or to reduce the monomers remaining in the copolymer, stripping may be conducted to recover the monomers.
Then, to this sUspensioll system, an aromatic amine and ammonia 25 are added to convert the maleic anhydride residue of the copolymer to its imide. The total moles of the arolllntic amine and amlllonia to be added are preferably from 0. 8 to 1. 5 times the moles of the maleic anhydride used. The moles of the aromatic amine are required to be ~237~
greDter than the moles of t]le ammonia. If the moles of the added amine exceeds 1.5 times, unreacted amine will remain in the composition thus obtained, and if it is less than 0.8 time, the conversion to imide will be inadequate, such being undesir1ble. The 5 reaction temperature for the con-~ersion to imide is preparably from 120 to 160C, and the reaction time is preferably from 0 . 5 to 3 hours .
The ammonia m~y be added in the form of a gas or an aqueous solution (i . e . aqueous ammonia) .
Thus, a heat resistant resin composition in the forrn of partic'les 10 (beads) wherein the copolymer A and the copolymer B are ulliformly mixed, is obtainable. According to the process of the present invention, it is unnecessary to use the N-aromatic maleimide and male-imide which are e~pensive and which are not prepared by mass-production, and it is unnecessary to mechanically kneading the 15 copolymer A and the copolymer B since the product is obtainable in the form wherein such copolymers are already uniformly mixed. ~hus, industrial merit of this process is extremely great.
Now, the present invention will be described in furtller detail with reference to Examples. Various ph~-Tsical properties of the 20 compositions ~vere measured in accordallce ~Yith the l'ollo~ving methocls.
Tensile strength and Izod impact streng~th: JIS K-6871 Heat resistance (Vicat softening point): JIS K-6870 High temperature stability~ A test piece was maintained in a gear oven at 270C for 1 hour, whereupon the presence or absence 25 of foaming and the weight reduction were measured.
E~ ample 1:
Into a 20 " autoclave, 5710 g of styrene and 189 g of maleic ~nhydride vere fed, and the tcmperature ~vas raised to 110C urlder stirring in a nitrogen Dtmosphere. ~Yhile contilluously adding to this - 8- ~Z37~4 system liquid maleic anhydride in a total amount of 1143 g maintained at a temperature of 70C at a supply rate as shown in the follo~ving Table 1, bulk polymerization was conducted at 110C fo-r 220 minutes.
At the completion of the continuous addition, the conversion 5 was 55% by weight and the content of the maleic anhydride residue in the resulting copolymer was 33%. To this system, 1200 g of acrylonitrile was added in 20 minutes, while lowering the temperature of the system to 95C, and the stirring was continued for further 10 minutes at this temperature. At this stage, the concentration of the 10 malelc anhydride in the monomers was not more than 0.1%.
To this system, 3 g of a polyvinyl alcohol-ty~e suspension agent, 3 g of a polyacrylic acid ester-type suspension agent and 6500 g of water containing 30 g of sodium sulfate were added to bring the system in a suspension state. To this suspension, 4 g of azobisiso-15 butyronitrile was added, and polymeri~ation was conducted at 80C for90 minutes. The temperature was raised to 150C in 60 minutes, and stripping was conducted for 60 minutes ~t tllis temperature. Then, 1140 g of aniline and 116 g of 30% aqueous ammonia were added thereto, and the reaction for the conversion to imide was conducted at a 20 temperature of 155C for 120 minutes. The obtained polymer in the form of beads was washed with water and then dried.
The beads were analyzed and found to be amixture comprising 58%
by weight of a copolymer A composed of 30% of the N-phenylm~qleimide residue, 3Po of tlle maleimide residue and 67% of the styrcne residue, and 25 42% by ~Yeight of a copolymer B composed of 40% of the acrylonitrile res.due and 60~o of the styrene residue.
The beads were pelletized by a 1 inch extruder equipped with a vent, and then formed into test pieces by a 1 ounce injection molding machine. Various physical properties of the test pieces ~Yere evaluated, 9- 1237Z;~4 and the results are shown in Table 2.
Table 1 Supply rate of maleic anhydride Tirne (min.) Supply rate (g/min.) Total amount (g) __ _ _ 0 7.0 0 5.9 388 120 5.0 715 180 4.2 9~2 220 3.8 1,143 10 Example 2:
Beads were prepared in the same manner as in Example 1 except that the amount of aniline was changed to S85 g and the amount of 30% aqeous ammonia was changed to 270 g.
The composition of the beads was found to be a mixture comprising 15 57% by weight of a copolymer A composed of 23% of the N-phenylmale-imide residue, lO~o of the maleimide residue and 67% of the styrene residue, and 43% by weight of a copolymer B composed of 40% of the acrylonitrile residue and 60% of the styrene residue. Tlle physical properties are shown in Table 2.
20 Example 3:
64 parts l~y weight of the pellets of Example 2 were mixed with 36 parts by weight of an ABS resin (styrene rcsidue: 49% by weight, acrylonitrile residue: 17% by weight, and butadiene residue: 34% by weight) prepared by emulsion polymerization, and the mixture was 25 pelletized and formed into test pieces. Various ph~sical properties 1~3~
of the test pieces were evaluated. The results thereby obtained are shown in Table 2.
Comp arative Example 1:
Beacls were prepared in the same manner as in Example 1 except 5 that no aniline and no nmmonia were added.
The composition of the beads was found to be a mixture comprising 53% by weight of S~IA composed of 33% of the maleic anhydride residue and 67% of the styrene residue, and 47% by weight of a copolymer B
composed of 40% of the acrylol~itrile residue and 60% of the styrene 10 residue. The pl~ysical properties are shown in Table 2.
Comparative Example 2:
Beads were prepared in the same manner as in Example 1 except that the amount of aniline was changed to 506 g, and the amount of 30% aqueous ammonia was changed to 500 g.
The composition of the beads was found to be a mixture comprising 55% by weight of a copolymer composed of 13% of the N-phenylmçlleimide residue, 20% of the maleimide residue and 67% of the styrene rcsidue, and 45% by weight of a copolymer B composed of ~0% of the acrylonitrile residue and G0% of the styrene residue. The physical properties are 20 sho~Yn in Table 2. ~1hile the test pieces of Examples 1 and 2 were transparent, the test pieces of this Comparative E~ample vere opaque, thus indicating that the compatibility of the copolymers A and B was lost .
Comparative Example 3:
~larig~ls pro~?ertie~_of the commercially available AS resin (SAN-C
'`~t ~ ~ O r n~ntu~-y Mitsubishi l~qonsanto Chemical Company) were evaluated, and the results are shown in Table 2.
- 11- 12~37'~4 Comparative Example 4:
46 parts by weight of the A~ resin used in Comparative Example 3 was mixed with 36 parts by weight of the ABS resin used in Example 3, and the mixture was pelletized and then formed into test pieces.
Various physical properties of the test pieces were evaluated. The results thereby obtailled are shown in Table 2.
Comparative Example 5:
A composition was obtained in the same manner as in Example 1 except that the amount of aniline was changed to 1260 g, and the 10 amount of 30% aqueous ammonia was changed to 0.
This composition was found to be a mixture comprising 58% by weight of a copolymer composed of 31% of the N-phenylmaleimide residue,
~Z3~
IIF,AT RESISTANT RESIN COl~qPOSlTlON
Tl~e pres~nt irl~ntiorl relates to a heat resistallt rcsin composition havillg a high thermal deformation temperature and a hig]l thermal decomposition temperature.
A copo]ymer (SMA) of a vinyl aromatic monomer with maleic 5 anhydride has a high theImal deformation temperature and good compatibi]ity wit]l other thermoplclstic resins such as a styrene-acrylollitrile copolyrner (AS resin), and it is useful for the preparation of a heat resistant resin cornposition.
However, S~1A is infeLior in its stability at a high temper~ture, l0 and it has drawbacks that when heated at a temperature of 230C or il;g]ler, it tends to lead to foaming or weight reduction and it is likely to undergo cross-linking, w]lereby the molding processability of the resin composition contaillillg Sl\~A is considerably impaired. It has been attempted to improve the high temperature stability of SMA by 15 incorpoI ating various additives such as anti-oxidants, but no satis-factory results have been obtained. The present inve]ltors have condllcted extensive rescarches with an aim to overcome the above-mel1tiollcd drawbacks and to present A heat resistault resin composition containing a copolymer composed of a vinyl aromatic monomer and a 20 maleic acid derivative and havillg a high temperature stability and a high thel mal dcformation temperature. As a result, the present ~7;~24 invention has been accolllp]ished.
Namely, the above~mcl-tioned object of the present invention hns bcell attnined by a heat resistallt r esin composition comprising fZom 10 to 90% by ~veight of a copolymer A and from 90 to 10~ by wcight of a copolymer B, in ~V]liC]I the copolymer A is composed of an N-arofnatic mal~imide monolller rcsi(lue, a mn]cimide monomer rcsidue, a vinyl aromatic mo7l0lller residue nnd, optionally other vinyl monomer residue, t]le total ~or~tent of the N - aromntic maleimide monomer residue and the malciinide monomer r esidue bcing from 10 to 45%, the content of the N-aromatic m~lcimide monomer residue being grcater than the content of the maleimide monomer residue, the content of the vinyl aromatic monomcr residue being from 90 to 55% and the content - of s~lid other vinyl monomer residue being from 0 to 20%, and the copolymer B is composed of a vinyl cyanide monolller residue, a vinyl aromatic monomer rcsidue and, optionally other vinyl monomer residue, the content of the vinyl cyanide monomer residue being from 20 to 55%, the content of v-inyl aromatic mollolner residue bcing from 80 to 45% and the content of said other vinyl monomer residue beïng from 0 to 20o.
In the prcscllt invclltion, the content of each monolller residlle is represented by a proportion by percentage of the number of units of the monomer residue to the total number of units of val~ious monomer r esidues contailled in the copoiymer conccrned.
- 3- ~2~722~
Now, the present invention will be described in detail with reference to the preferred embodiments.
As the villyl aromatic compound to be used in the present invention, styrene is most common, but other compounds such as 5 ~-methylstyrene, p-methylstyrene, t-butylstyrene, a styrene halogenide or a mixture thereof may be used. As the vinyl cyanide compound, acrylonitrile, Methacrylonitrile or a mixture thereof is usually used.
The N-aromatic maleimide may be obtained by condensing a primary aromatic amine with fumaric acid, maleic acid, maleic acid 10 anhydride or other maleic acid derivatives. As the p1imary aromatic amine, aniline or an aniline derivative with its benzene ring substituted by an alkyl group, a halogen atom or a nitro group, such as toluidine or nitroaniline is used. Further, phenylenediamine or c~-naphthylarnine may also be used. These amines may be used alone or in combination 15 as a mixture of two or more different kinds. The maleimide may be obtained by condensing a maleic acid derivative such as maleic acid anhydlide, ~vith ammonia. The copolymer A may be produced by copolymelizing an N-aromatic maleimide with other monomers. Ilowever, as will be mentioned hereinafter, it is preferred to employ a method 20 wherein a maleic acid anhydride copolymer is reacted witll the above-mentioned amine and ammonia during the polymerization step or in a separate step to convert it into an imide, since this method is simple and the required monomers are readily available.
The content of the N-aromatic maleimide in the copolymer A
25 must be greater than the content of the maleimide. Otherwise, the compatibility of the copolymer A with the copolymer B will be poor, thus leading to an infcrior physical properties of the resin composition thereby obtained. ~Vithin the above-mentioned r~lge, the greater _ 4_ ~2~7~24 the content of the maleimide residue is, the higher the thermal deformation temperature becomes.
The total content of the N-aromatic maleimide residue and the maleimide residue contained in the copolymer A should be from 10 to 5 45%. If the total amount exceeds 45%, the flo~vability tends to decrease and the mo]ding opcration becomes difficult. On the other hand, if tlle total amount is less than 10%, no adequate improvement of the thermal deformalion temperature is obtainable.
Further, the content of the vinyl aromatic monomer residue should 10 be from 90 to 55%. If the content of the vinyl aromatic monomer residue increases, the flowability will be improved, but the thermal deformation temperature decreases.
A part of the vinyl aromatic monomer residue may be replaced by other monomer, for instance, a vinyl cyanide monomer such as 15 acrylonitrile or methacrylonitrile, an ester of acrylic acid or metha-acrylic acid such as methylacrylate or methylmethacrylate, or a derivative of maleic acid or fumaric acid such as maleic anhydlide, dimethyl maleataor dimethyl fumarate, as the case requires. In such a case, the content of the other monomer for replacemellt should be 20 at most 20%. If the content exceeds 20%, the compatibility with other styrene-type resin is likely to be inferior.
- Adequate compatibility with the copolymer A will be obtained if the content of the vinyl cyanide monomer residue in the copolymer B
is within a ran~e of from 20 to 55%, the rest being the vinyl aromatic 25 monomer residue, A part of the ~,inyl aromatic monomer residue may preferably be substituted by other vinyl monomer such as an ester of acrylic acid or methacrylic acid, as the case requires. In such a case, the _ 5- ~Z~7~2~
content of said other vinyl monomer residue sllould preferably be at most 20%, whel-eby no adverse effects will be imparted to the compatibility with other resins.
The composition according to the present invention is superior 5 in the heat resistance, high temperature stability, solvent resistance and ~lowabilitv during the molding operation. Further, the composi-tion of the present invention has good compatibility with an ABS resin, a MBS resin, an AES resin, an ACS resin or an AAS resin, and accord-ingly it is possib]e to improve the shock resistance by incorporating such 10 resins. In such a case, it is readily possible to bling the thermal deform-ation temperature (a Vicat softening point) to at least 115C. Further, a reinforcing material or fiiler such as g]ass fiber, carbon fiber, ta]c or calcium carbonate, or other additives may be incoporated.
Now, the process of the present invention will be described.
15 Firstly, bulk polymerization is conducted whi]e continuously supplying maleic acid anhydride in the presence of the vinyl aromatic monomer.
The amount of the maleic acid anhydride monomer to be added here is preferably rom 10 to 45 molar %. The polymelization temperature is preferably from 90 to 130C, and no polymerization initiator may be 20 required. The conversion in this step is at ]east 10% by ~veight and can be increased as far as the stirring driving i`orce of the polymerization apparatus permits. The polymelization time is determilled depending upon the conversion, the polymerization temperature, the concentration of the maleic acid anhydlide, and is usually within 25 a range of from 1 to 10 hours. After completion of the continuous supply o~ tlle maleic acid anllydlide, the maleic acid anllydIide in the monomer mixture will rapidly be consumed, ~vhereupon the system becomes in the form of a syrup composed substantially of the copolymer - 6- ~Z~7~2~
and the vinyl aromatic monomer. A part of the vinyl aromatic compound to be initially present rnay be replaced by an ester of acrylic acid, an ester of methacrylic acid or a vinyl cyanide compound.
To this syrup, a vinyl cyanide monomer is added and uniformly 5 mixed. The amount of the addition is adjusted to bring the content of the vinyl c:yan;de monolller residue in tlle copolymer formed by the reaction with the remaining vinyl aromatic compound to a level of from 20 to 55%.
This syrup is suspended in water, alld the vinyl aromatic monomer 10 and the vinyl cyanide monomer are co-polymerized by suspension polymerization. A conventional polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide may be used. Likewise, the suspension agent may be a conventional one such as polyvinyl alcohol, polyacrylamide or barium sulfate. The polymerization temper-15 ature is usually within a range of from 60 to 160C, and thepolymerization time is determined depending upon the polymerization temperature and the type and amount of the initiator, but, is usually within a range of from 1 to 10 houls. In order to maintain the content of the vinyl cyanide monomer residue in the resulting copolymer to be 20 constant, the vinyl aromatic monomer or the vinyl cyanide rnonomer may be added continuously or intermittently. Further, in order to reduce tlle amount of the resulting copolyrner or to reduce the monomers remaining in the copolymer, stripping may be conducted to recover the monomers.
Then, to this sUspensioll system, an aromatic amine and ammonia 25 are added to convert the maleic anhydride residue of the copolymer to its imide. The total moles of the arolllntic amine and amlllonia to be added are preferably from 0. 8 to 1. 5 times the moles of the maleic anhydride used. The moles of the aromatic amine are required to be ~237~
greDter than the moles of t]le ammonia. If the moles of the added amine exceeds 1.5 times, unreacted amine will remain in the composition thus obtained, and if it is less than 0.8 time, the conversion to imide will be inadequate, such being undesir1ble. The 5 reaction temperature for the con-~ersion to imide is preparably from 120 to 160C, and the reaction time is preferably from 0 . 5 to 3 hours .
The ammonia m~y be added in the form of a gas or an aqueous solution (i . e . aqueous ammonia) .
Thus, a heat resistant resin composition in the forrn of partic'les 10 (beads) wherein the copolymer A and the copolymer B are ulliformly mixed, is obtainable. According to the process of the present invention, it is unnecessary to use the N-aromatic maleimide and male-imide which are e~pensive and which are not prepared by mass-production, and it is unnecessary to mechanically kneading the 15 copolymer A and the copolymer B since the product is obtainable in the form wherein such copolymers are already uniformly mixed. ~hus, industrial merit of this process is extremely great.
Now, the present invention will be described in furtller detail with reference to Examples. Various ph~-Tsical properties of the 20 compositions ~vere measured in accordallce ~Yith the l'ollo~ving methocls.
Tensile strength and Izod impact streng~th: JIS K-6871 Heat resistance (Vicat softening point): JIS K-6870 High temperature stability~ A test piece was maintained in a gear oven at 270C for 1 hour, whereupon the presence or absence 25 of foaming and the weight reduction were measured.
E~ ample 1:
Into a 20 " autoclave, 5710 g of styrene and 189 g of maleic ~nhydride vere fed, and the tcmperature ~vas raised to 110C urlder stirring in a nitrogen Dtmosphere. ~Yhile contilluously adding to this - 8- ~Z37~4 system liquid maleic anhydride in a total amount of 1143 g maintained at a temperature of 70C at a supply rate as shown in the follo~ving Table 1, bulk polymerization was conducted at 110C fo-r 220 minutes.
At the completion of the continuous addition, the conversion 5 was 55% by weight and the content of the maleic anhydride residue in the resulting copolymer was 33%. To this system, 1200 g of acrylonitrile was added in 20 minutes, while lowering the temperature of the system to 95C, and the stirring was continued for further 10 minutes at this temperature. At this stage, the concentration of the 10 malelc anhydride in the monomers was not more than 0.1%.
To this system, 3 g of a polyvinyl alcohol-ty~e suspension agent, 3 g of a polyacrylic acid ester-type suspension agent and 6500 g of water containing 30 g of sodium sulfate were added to bring the system in a suspension state. To this suspension, 4 g of azobisiso-15 butyronitrile was added, and polymeri~ation was conducted at 80C for90 minutes. The temperature was raised to 150C in 60 minutes, and stripping was conducted for 60 minutes ~t tllis temperature. Then, 1140 g of aniline and 116 g of 30% aqueous ammonia were added thereto, and the reaction for the conversion to imide was conducted at a 20 temperature of 155C for 120 minutes. The obtained polymer in the form of beads was washed with water and then dried.
The beads were analyzed and found to be amixture comprising 58%
by weight of a copolymer A composed of 30% of the N-phenylm~qleimide residue, 3Po of tlle maleimide residue and 67% of the styrcne residue, and 25 42% by ~Yeight of a copolymer B composed of 40% of the acrylonitrile res.due and 60~o of the styrene residue.
The beads were pelletized by a 1 inch extruder equipped with a vent, and then formed into test pieces by a 1 ounce injection molding machine. Various physical properties of the test pieces ~Yere evaluated, 9- 1237Z;~4 and the results are shown in Table 2.
Table 1 Supply rate of maleic anhydride Tirne (min.) Supply rate (g/min.) Total amount (g) __ _ _ 0 7.0 0 5.9 388 120 5.0 715 180 4.2 9~2 220 3.8 1,143 10 Example 2:
Beads were prepared in the same manner as in Example 1 except that the amount of aniline was changed to S85 g and the amount of 30% aqeous ammonia was changed to 270 g.
The composition of the beads was found to be a mixture comprising 15 57% by weight of a copolymer A composed of 23% of the N-phenylmale-imide residue, lO~o of the maleimide residue and 67% of the styrene residue, and 43% by weight of a copolymer B composed of 40% of the acrylonitrile residue and 60% of the styrene residue. Tlle physical properties are shown in Table 2.
20 Example 3:
64 parts l~y weight of the pellets of Example 2 were mixed with 36 parts by weight of an ABS resin (styrene rcsidue: 49% by weight, acrylonitrile residue: 17% by weight, and butadiene residue: 34% by weight) prepared by emulsion polymerization, and the mixture was 25 pelletized and formed into test pieces. Various ph~sical properties 1~3~
of the test pieces were evaluated. The results thereby obtained are shown in Table 2.
Comp arative Example 1:
Beacls were prepared in the same manner as in Example 1 except 5 that no aniline and no nmmonia were added.
The composition of the beads was found to be a mixture comprising 53% by weight of S~IA composed of 33% of the maleic anhydride residue and 67% of the styrene residue, and 47% by weight of a copolymer B
composed of 40% of the acrylol~itrile residue and 60% of the styrene 10 residue. The pl~ysical properties are shown in Table 2.
Comparative Example 2:
Beads were prepared in the same manner as in Example 1 except that the amount of aniline was changed to 506 g, and the amount of 30% aqueous ammonia was changed to 500 g.
The composition of the beads was found to be a mixture comprising 55% by weight of a copolymer composed of 13% of the N-phenylmçlleimide residue, 20% of the maleimide residue and 67% of the styrene rcsidue, and 45% by weight of a copolymer B composed of ~0% of the acrylonitrile residue and G0% of the styrene residue. The physical properties are 20 sho~Yn in Table 2. ~1hile the test pieces of Examples 1 and 2 were transparent, the test pieces of this Comparative E~ample vere opaque, thus indicating that the compatibility of the copolymers A and B was lost .
Comparative Example 3:
~larig~ls pro~?ertie~_of the commercially available AS resin (SAN-C
'`~t ~ ~ O r n~ntu~-y Mitsubishi l~qonsanto Chemical Company) were evaluated, and the results are shown in Table 2.
- 11- 12~37'~4 Comparative Example 4:
46 parts by weight of the A~ resin used in Comparative Example 3 was mixed with 36 parts by weight of the ABS resin used in Example 3, and the mixture was pelletized and then formed into test pieces.
Various physical properties of the test pieces were evaluated. The results thereby obtailled are shown in Table 2.
Comparative Example 5:
A composition was obtained in the same manner as in Example 1 except that the amount of aniline was changed to 1260 g, and the 10 amount of 30% aqueous ammonia was changed to 0.
This composition was found to be a mixture comprising 58% by weight of a copolymer composed of 31% of the N-phenylmaleimide residue,
2% of the maleic anhydride residue and 67% of the styrene residue.and 42% by weigm of a copolymer composed of 40% of the acrylonitrile residue and 60% of the styrene residue. The ph~sical proper.ies of the test pieces of this Comparative Example are shown in Table 2.
In the case where no maleimide residue was present, the Vicat softening point decreased by about 10C as compared with the case where the maleimide residue is present.
~0 Comparative Exalllple 6:
A composition was obtained in the same manner as in Example 1 except that the amount of aniline was changed to 0 and the amount of 30% aqueous ammollia was changed to 770 g.
This composition was foulld to be a mixture comprising of 53% by weight of a copolymer A composed of 29% of the maleimide residue, 4%
of the maleic anhydride residue and G7% of the styrene residue, and 47% by weight of a copolymer B composed of 40% of the acrylonitrile residlle and (;0% of the styrene residue.
- 12- ~Z3~2~
The test pieces containing no N-phenylmaleimide residue was opaque and brittle, and the compatibility of the copolymers A and B
was thereby completely lost.
T able 2 __ _ _ _ _~
_ _ F,xampl~ s Comparative Examp]e , , _ ~_ 1 ~ 2 1 3 _ ~ _ 2-- 3 j_~ 5 Tensile strength 680 G80 500 670 610 720 470 700 ( K g /cm2 ) _ _ ,___ ____ _ I ~od impact strengh 1 4 1. 4 14 . 0 1. 3 0 . 9 1. 8 15 . 0 1. 5 (Kg cm /cm) __ __ i _ _ point (C) 133 137 123 131 136 100 98 125 _ _ ~ _ _ igh temperature stability Foaming No No No Yes No No No No ~1eight reduction 0.9 L.9 1.0 1 3 8 L~ L__ ~ 1 o
In the case where no maleimide residue was present, the Vicat softening point decreased by about 10C as compared with the case where the maleimide residue is present.
~0 Comparative Exalllple 6:
A composition was obtained in the same manner as in Example 1 except that the amount of aniline was changed to 0 and the amount of 30% aqueous ammollia was changed to 770 g.
This composition was foulld to be a mixture comprising of 53% by weight of a copolymer A composed of 29% of the maleimide residue, 4%
of the maleic anhydride residue and G7% of the styrene residue, and 47% by weight of a copolymer B composed of 40% of the acrylonitrile residlle and (;0% of the styrene residue.
- 12- ~Z3~2~
The test pieces containing no N-phenylmaleimide residue was opaque and brittle, and the compatibility of the copolymers A and B
was thereby completely lost.
T able 2 __ _ _ _ _~
_ _ F,xampl~ s Comparative Examp]e , , _ ~_ 1 ~ 2 1 3 _ ~ _ 2-- 3 j_~ 5 Tensile strength 680 G80 500 670 610 720 470 700 ( K g /cm2 ) _ _ ,___ ____ _ I ~od impact strengh 1 4 1. 4 14 . 0 1. 3 0 . 9 1. 8 15 . 0 1. 5 (Kg cm /cm) __ __ i _ _ point (C) 133 137 123 131 136 100 98 125 _ _ ~ _ _ igh temperature stability Foaming No No No Yes No No No No ~1eight reduction 0.9 L.9 1.0 1 3 8 L~ L__ ~ 1 o
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A heat resistant resin composition comprising from 10 to 90% by weight of a copolymer A and from 90 to 10% by weight of a copolymer B, in which the copolymer A is composed of an N-aromatic maleimide monomer residue, a maleimide monomer residue, a vinyl aromatic monomer residue and, optionally other vinyl monomer residue, the total content of the N-aromatic maleimide monomer residue and the maleimide monomer residue being from 10 to 45%, the content of the N-aromatic maleimide monomer residue being greater than the content of the maleimide monomer residue, the content of the vinyl aromatic monomer residue being from 90 to 55% and the content of said other vinyl monomer residue being from 0 to 20%, and the copolymer B is composed of a vinyl cyanide monomer residue, a vinyl aromatic monomer residue and, optionally other vinyl monomer residue, the content of the vinyl cyanide monomer residue being from 20 to 55%, the content of the vinyl aromatic monomer residue being from 80 to 45% and the content of said other vinyl monomer residue being from 0 to 20%.
2. The heat resistant resin composition according to Claim 1 wherein the vinyl aromatic monomer residue is a residue derived from a vinyl aromatic compound selected from the group consisting of styrene, .alpha.-methyl styrene, p-methyl styrene, t-butyl styrene, a styrene halo-genide and a mixture thereof.
3. The heat resistant resin composition according to Claim 1 wherein the vinyl cyanide monomer residue is a residue derived from a vinyl cyanide compound selected from the group consisting of acrylonitrile, methacrylonitrile and a mixture thereof.
4. The heat resistant resin composition according to Claim 1 wherein the N-aromatic maleimide residue is a residue of N-aromatic maleimide obtained by condensation of a primary aromatic amine with fumaric acid, maleic acid, maleic acid anhydride or other maleic acid derivative.
5. The heat resistant resin composition according to Claim 4 wherein the primary aromatic amine is selected from the group consisting of aniline, toluidine, nitro aniline, phenylenediamine and .alpha.-naphthyl amine.
6. The heat resistant resin composition according to Claim 1 wherein the maleimide monomer residue is a residue derived from maleimide obtained by condensation of ammonia with maleic acid anhydride.
7. The heat resistant resin composition according to Claim 1 wherein said other vinyl monomer residue is a residue derived from a monomer selected from the group consisting of acrylonitrile, methacrylonitrile, rnethyl acrylate, methyl methacrylate, maleic acid anhydride, dimethyl maleate and dimethyl fumarate.
8. A process for preparing a heat resistant resin composition which comprises bulk-polymerising a vinyl aromatic monomer with from 10 to 45 molar % of a maleic acid anhydride monomer to obtain a syrup composed substantially of a first copolymer and an unreacted vinyl aromatic monomer, adding a vinyl cyanide monomer to this syrup in such an amount that the content of the vinyle cyanide monomer residue in a second copolymer to be formed by its reaction with the unreacted vinyl aromatic monomer becomes from 20 to 55%, subjecting the mixture to suspension polymerization to polymerize the unreacted vinyl aromatic monomer with the vinyl cyanide monomer to form the second copolymer, then adding an aromatic amine and ammonia to the suspension system in a total amount by mole of from 0.8 to 1.5 times the amount by mole of the maleic acid anhydride to convert the maleic acid anhydride residue in the first copolymer to its imide.
9. The process according to Claim 8 wherein the amount by mole of the aromatic amine is greater than the amount by mole of the ammonia.
10. The process according to Claim 8 wherein the bulk-polymerization is conducted at a temperature of from 90 to 130°C for from 1 to 10 hours.
11. The process according to Claim 8 wherein the suspension polyme-rization is conducted at a temperature of from 60 to 160°C for from 1 to 10 hours.
12. The process according to Claim 8 wherein the reaction to convert the maleic anhydride residue to its imide is conducted at a temperature of from 120 to 160°C for from 0.5 to 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000442902A CA1237224A (en) | 1983-12-08 | 1983-12-08 | Heat resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000442902A CA1237224A (en) | 1983-12-08 | 1983-12-08 | Heat resistant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1237224A true CA1237224A (en) | 1988-05-24 |
Family
ID=4126702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000442902A Expired CA1237224A (en) | 1983-12-08 | 1983-12-08 | Heat resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1237224A (en) |
-
1983
- 1983-12-08 CA CA000442902A patent/CA1237224A/en not_active Expired
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