CA1196123A - Glass-filled thermoplastic resins - Google Patents
Glass-filled thermoplastic resinsInfo
- Publication number
- CA1196123A CA1196123A CA000414195A CA414195A CA1196123A CA 1196123 A CA1196123 A CA 1196123A CA 000414195 A CA000414195 A CA 000414195A CA 414195 A CA414195 A CA 414195A CA 1196123 A CA1196123 A CA 1196123A
- Authority
- CA
- Canada
- Prior art keywords
- group
- resin
- monovinylidene
- composition
- copolymer
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
Abstract
IMPROVED GLASS-FILLED THERMOPLASTIC RESINS
Abstract:
Glass fiber reinforced thermoplastic resins composing glass fiber, a thermoplastic resin and a copolymer of an ethylenically-unsa-turated monomer and from about 1 to about 20 wt.% of copolymerizable functional monomer exhibit a marked improvement in impact proper ties, heat distortion values and ductil-ity.
Abstract:
Glass fiber reinforced thermoplastic resins composing glass fiber, a thermoplastic resin and a copolymer of an ethylenically-unsa-turated monomer and from about 1 to about 20 wt.% of copolymerizable functional monomer exhibit a marked improvement in impact proper ties, heat distortion values and ductil-ity.
Description
IMPROVED GLASS-FILLED THERMOPLASTIC P~ESINS
Description This invention rela~es to improved glass fiber reinforced thermopla~tic resins and more particularly to improved compositions comprisinq glass fiberr a thermoplastic resin and a copolymer of at least one ethylenically-un~
s~turated monomer and a copolymerizable func-tional monomer and to a method for enhancing the impact propertie~ of glass fiber reinforced thermoplastic resinsO
Glass fiber reinforcement is added to a variety of plastic matricies to improve the strength, dimensional stability and heat resis-tance of the composite. The addition of rein-forcing fibers in the form of chopped or milled glass strand to thermoplastic molding resins enhances stiffness, reduces creep and improves overall dimensional stability of molded parts, particularly at elevated temperatures. To be effective in molding resins the glass fiber surfaces normally must be treated with a coup-ling agent to improve adhesion between the fiber and the matrix resin, and a wide variety of ~5 silane compounds have been developed ~or this purpose. Glas~ fibers treated with appropriate coupling agents have been employed to reinforce a wide variety of thermoplastics including polyamide (nylos~ and polypropylene. Where the matrix resin is crys~alline as in nylon, for ~xample, marked increases .in f lexural strength, rigidity and impact resistance are noted, ~owever9 in rigid amorphous molding resins such as polystyrene and styrene-acrylonitrile copoly-5 mers which are generally more brittle in charac-ter ~ the addition of chopped or milled glass fiber nornnally results only in an increase in rigidity, flexural modulus and tensile strength without imprsving the generally low impact 10 strength of the matrix resin. These glass filled composites are thus more brittle and less ductile than the corresponding unfilled counter-parts. An improved method for reinforcing such brittle amorphous resins which would result in 15 both improved dimensional stability and in-creased impact strength and ductility would ~hus be a useful advance in the art.
The instant invention is an improved composition comprising glass fiber,a thermoplas-20 tic resin and a copolymer of an ethylenically-unsaturated monomer and a copolymerizable functional monomer and a method for improviny the impact properties of glass reinforced thermoplastic resins.
The glass reinforced thermoplastic resin compositions which are improved by the practice of this invention comprise from 5 to 50 wt.~ glass iber and from 9S to 50 wto % Of a rigid thermoplastic resin. The rigid thermo-30 plastic resin may be any of the widely known 0801g2-M ~ 3 ~
rigid amorphous thermoplastic molding resins.
More particularly~ the thermoplastic re~ins useful for the purposes of this invention are glass filled monovinylidene resins and may 5 be selected ~rom he group consisting of sty-renic resins and acrylic resins including for example polystyrene, polymethyl-methacrylate styrene-acrylonitrile copolymer resins, copoly-mers of styrene, alphamethylstyrene and acrylon-10 itrile, ~tyrene-methylmethacrylate copolymers7 styrene -maleic anhydride copolymers and the like. Also useful are hi~h impact, rubber-modi-fied graft and blend polymer analogs of these resins including rubber-modified high impac~
15 polystyrenes (~IPS~ and rubber modified styrene-acrylonitrile graft copolymers such as the ABS
and ASA resins, The compositions may further include other compatible resins known in the resin molding art a~ exemplified by blends of 20 polyphenylene oxide with high impact styrene.
These thermoplastic resins are well known and widely available in both glass filled and unfilled form and the preparation thereof does not form a part of this inventionO
The compositions of this invention further comprise a copolymer of an ethyleni-cally~unsaturated monomer and a copolymeri~able functional monomer. More particularlyl the copolymer is formed of a monovinylidene monomer 30 selected from the ~roup consisting of monovinyl aromatic compounds such as styrene, alpha methylstyrene, vinyl toluene and the like7 080192~M - 4 -acryli~ compounds such as a lower alkyl acry-late, acrylonitrile~ acrylamide and ~he like, methacrylic compounds such as alkyl methacry-lates, methacrylamide and methacrylonitrile, as well as mixtures and combinations thereof ~ and a copolymerizable functional monomer defined as a monoethylenically unsatura~ed monomer ccntaining at least one reactive functional radical. The fllnctional radical may be selected from the 10 group consisting of epoxy radicals, and carbonyl radicals such as carboxylic acid radicals, carboxylic anhydride radicals, amide radicals~
N-alkoxyalkyl amide radicals and the like.
Examples of such functional monomers include 15 acrylic acid, maleic anhydride~ glycidyl meth-acrylate~ N-methylol-acrylamide and N-butoxyme-thylacrylamide. The copolymers useful for the purposes of this invention may be readily prepared by any of a variety of free radical processes including emulsion, suspension and bulk polymeriæation processes. The amount of functional monomer employed in preparing the copolymer will vary accordin~ to the particular end use envisioned, however in ~ener~l the polymer will consist of from about 1 to about 20 wt,~, based on final copolymer, of functional monomer units and correspondingly from about 99 - to about 80 wt.% of ethylenically-unsaturated monomer units.
z~
080192-M ~ S -The copolymer is employed in blends with the glass filled thermoplastic resin to enhance the impact properties of the glass fiber reinforced resin. The blends may be formed by any of the methods commonly employed in the compounding art fcr producing glass filled resins including dry blending, melt mixing, extrusion coating of coritinuous f iber and the like. Alternatively~ one or more of the xesin components may be used in latex form to coat the fiber to produce resin coated fiber for use in preparing qlass f illed composites. Proper selection of the particular compounding process for making blends for specific end uses will be readily apparent to those skilled in the com-pounding art. The amvunt of copolymer employed will depend in part upon the level of functional radical containing monomer units present in the copolymer, in that copolymers containing higher levels of Eunctional radical monomer units will be effective even when blen~ed with the glass filled thermoplastic resin at low levels. However, the levels which produce effective impact improvement will be from about 1 wt.~ to about 20 wt.% of the final composi-tion.
The practice of this invention will be better understood by consideration of the following Examples which illus~rate ~he prepara-tion of the copolymer and the use thereof inglass reinforced thermoplas~ic compositionsO
.
Description This invention rela~es to improved glass fiber reinforced thermopla~tic resins and more particularly to improved compositions comprisinq glass fiberr a thermoplastic resin and a copolymer of at least one ethylenically-un~
s~turated monomer and a copolymerizable func-tional monomer and to a method for enhancing the impact propertie~ of glass fiber reinforced thermoplastic resinsO
Glass fiber reinforcement is added to a variety of plastic matricies to improve the strength, dimensional stability and heat resis-tance of the composite. The addition of rein-forcing fibers in the form of chopped or milled glass strand to thermoplastic molding resins enhances stiffness, reduces creep and improves overall dimensional stability of molded parts, particularly at elevated temperatures. To be effective in molding resins the glass fiber surfaces normally must be treated with a coup-ling agent to improve adhesion between the fiber and the matrix resin, and a wide variety of ~5 silane compounds have been developed ~or this purpose. Glas~ fibers treated with appropriate coupling agents have been employed to reinforce a wide variety of thermoplastics including polyamide (nylos~ and polypropylene. Where the matrix resin is crys~alline as in nylon, for ~xample, marked increases .in f lexural strength, rigidity and impact resistance are noted, ~owever9 in rigid amorphous molding resins such as polystyrene and styrene-acrylonitrile copoly-5 mers which are generally more brittle in charac-ter ~ the addition of chopped or milled glass fiber nornnally results only in an increase in rigidity, flexural modulus and tensile strength without imprsving the generally low impact 10 strength of the matrix resin. These glass filled composites are thus more brittle and less ductile than the corresponding unfilled counter-parts. An improved method for reinforcing such brittle amorphous resins which would result in 15 both improved dimensional stability and in-creased impact strength and ductility would ~hus be a useful advance in the art.
The instant invention is an improved composition comprising glass fiber,a thermoplas-20 tic resin and a copolymer of an ethylenically-unsaturated monomer and a copolymerizable functional monomer and a method for improviny the impact properties of glass reinforced thermoplastic resins.
The glass reinforced thermoplastic resin compositions which are improved by the practice of this invention comprise from 5 to 50 wt.~ glass iber and from 9S to 50 wto % Of a rigid thermoplastic resin. The rigid thermo-30 plastic resin may be any of the widely known 0801g2-M ~ 3 ~
rigid amorphous thermoplastic molding resins.
More particularly~ the thermoplastic re~ins useful for the purposes of this invention are glass filled monovinylidene resins and may 5 be selected ~rom he group consisting of sty-renic resins and acrylic resins including for example polystyrene, polymethyl-methacrylate styrene-acrylonitrile copolymer resins, copoly-mers of styrene, alphamethylstyrene and acrylon-10 itrile, ~tyrene-methylmethacrylate copolymers7 styrene -maleic anhydride copolymers and the like. Also useful are hi~h impact, rubber-modi-fied graft and blend polymer analogs of these resins including rubber-modified high impac~
15 polystyrenes (~IPS~ and rubber modified styrene-acrylonitrile graft copolymers such as the ABS
and ASA resins, The compositions may further include other compatible resins known in the resin molding art a~ exemplified by blends of 20 polyphenylene oxide with high impact styrene.
These thermoplastic resins are well known and widely available in both glass filled and unfilled form and the preparation thereof does not form a part of this inventionO
The compositions of this invention further comprise a copolymer of an ethyleni-cally~unsaturated monomer and a copolymeri~able functional monomer. More particularlyl the copolymer is formed of a monovinylidene monomer 30 selected from the ~roup consisting of monovinyl aromatic compounds such as styrene, alpha methylstyrene, vinyl toluene and the like7 080192~M - 4 -acryli~ compounds such as a lower alkyl acry-late, acrylonitrile~ acrylamide and ~he like, methacrylic compounds such as alkyl methacry-lates, methacrylamide and methacrylonitrile, as well as mixtures and combinations thereof ~ and a copolymerizable functional monomer defined as a monoethylenically unsatura~ed monomer ccntaining at least one reactive functional radical. The fllnctional radical may be selected from the 10 group consisting of epoxy radicals, and carbonyl radicals such as carboxylic acid radicals, carboxylic anhydride radicals, amide radicals~
N-alkoxyalkyl amide radicals and the like.
Examples of such functional monomers include 15 acrylic acid, maleic anhydride~ glycidyl meth-acrylate~ N-methylol-acrylamide and N-butoxyme-thylacrylamide. The copolymers useful for the purposes of this invention may be readily prepared by any of a variety of free radical processes including emulsion, suspension and bulk polymeriæation processes. The amount of functional monomer employed in preparing the copolymer will vary accordin~ to the particular end use envisioned, however in ~ener~l the polymer will consist of from about 1 to about 20 wt,~, based on final copolymer, of functional monomer units and correspondingly from about 99 - to about 80 wt.% of ethylenically-unsaturated monomer units.
z~
080192-M ~ S -The copolymer is employed in blends with the glass filled thermoplastic resin to enhance the impact properties of the glass fiber reinforced resin. The blends may be formed by any of the methods commonly employed in the compounding art fcr producing glass filled resins including dry blending, melt mixing, extrusion coating of coritinuous f iber and the like. Alternatively~ one or more of the xesin components may be used in latex form to coat the fiber to produce resin coated fiber for use in preparing qlass f illed composites. Proper selection of the particular compounding process for making blends for specific end uses will be readily apparent to those skilled in the com-pounding art. The amvunt of copolymer employed will depend in part upon the level of functional radical containing monomer units present in the copolymer, in that copolymers containing higher levels of Eunctional radical monomer units will be effective even when blen~ed with the glass filled thermoplastic resin at low levels. However, the levels which produce effective impact improvement will be from about 1 wt.~ to about 20 wt.% of the final composi-tion.
The practice of this invention will be better understood by consideration of the following Examples which illus~rate ~he prepara-tion of the copolymer and the use thereof inglass reinforced thermoplas~ic compositionsO
.
2~3 Example 1. Preparation of the Copolymer.
A polymerization kettle was charged with 81 g. of deionized wa~er, 0.06 9. of sodium dodecylbenzene sulfonate (23%) suractant and 0.23 g. of sodium carbonate. The charge was blanketed with ni~rogen, stirred and heated to 65 C. A monomer emulsion containing 81 9. of deionized water, 62.7 9. of styrene, 27.3 g. of acrylonitrile, 10.0 g. of N-isobutoxymethyl-acrylamide and 1.92 g. of the dioctyl ester of sodium sulfosuccinic acid was prepared by stirring the surfactant into the water, then adding the monomer.s slowly and with strong stirring. An initial char~e of 2.11 gO of the monomer emulsion was added to the kettle ollow-ed by a solution of 0035 g. of sodium persulfate in 3.85 9 of water as the initiator. The stirred mixture was heated at 65CC for 20 minO, then 0.5 g. of t dodecyl mercaptan (molecular weight regulator) were addedO The remaining monomer emulsion was then continuously added to the kettle over a three hour period while maintaining the nitrogen blanket and continua].ly heating and stirring the mixture at 65Co At the end of the addition of the monomer emulsion, the mixture was heated at 65C for an additional hour to complete the polymerization~ After cooling~ the polymer was collected by coa~ula-tion in three volumes of aqueous aluminumsulfate at 140F, filtering and washing the 6~3 080192-M ~ 7 -coagulated resin with water to remove surfac-tant~ The resin, amounting to ~8 g~ after dryiny, was a copolymer containing 6207%
wt.% styrene units, 27~3 wt.% acrylonitrile units and 10 wt.% M-isobutoxymethyl acrylamide unit~D
Example 20 Blends of Glass ~iber~
Thermoplastic Resin and Functional Copolymer.
A blend consisting of ~5 g. of granu lated ~tyrene-acrylonitrile resin~ obtained from Dow as Tyril*860, 20 9. of 1/4" chopped glass fiber, obtained from Owens Corning as B85 EB, and 15 9~ of powdered functional copolymer (see .Example 1) was prepared by dry-mixing the powdered resins and glass fiber.. The mixture was injection molded to provide test specimens.
The test ~pecimen exhibited a room temperature Xzod impact of 203 ft. lbs,~in. notch an~ a heat defle~tion temperature ~10 mil~ ~f 219~.
An injec~ion molded contrsl blend containing no funct~onal copolymer, prepared from ~0 ~0 of granulated styrene acrylonitrile resin and 20 gO of chopped 1/~" qlass fibert had an Izod impact of 1.0 ~t~ lbs./inO notch and a heat deflection temperature (10 mil~ of 212F~
It will thus be apparent from these data that the incorporation of 15 wt.~ of functional copolymer into ~ glass-filled sty-rene-acrylonitril~ resin provides a subs~antial improvement in impact properties and heat deflection temperature, , *trade mark Example 3 - 10~
In the followirlg Examples j, summarized in Table 1, functional copolymers containing from 2 to 10 wt. P6 N-isobutoxyme~hyl acrylamide 5 (IBMA) functional monomer uni~s and correspons3-ingly from 98 lto 90 wt. % styrene and acryloni-ltrile monomer units in a 2 0 3 :1 ratio were prepared substantially by the process of Example 19 then blended with styrene-acryloni-10 triie resin (Tyril 860) and 1/4'J chopped glass~Eiber ~ 885EB~ by milling on a two roll mill at 420F iEor 5 min.. The blend was sheeted-c:~u~, coo~ ed and then compression molded a~c 365~ F for 6 min. to form test spe~imens. The physi-~al 15 property data for the blends is reflected in Table I.
Control blends were prepare~l Iby milling and molding as for the specimens of Examples 3-10., ~~ * trade mark pa~loul UOISS~ldiL~ al~ S~ S
Sleq .8/1 pa~ 1~ ~edu}r P~ZI
'am~e~ uoF~a~IFQI 01 ~FSd ~SZ = La~ e~ep ~,s~ a~n~e~adi~3~ Ul~d (Z) odc~
L~ 0 WF~El~d~d 10~ d~x;~ pFulel~e ~ olnqosl-N ~ ~I (1) :5~ N
-ZI 866 I'll 66 6 0 - - OZ 08 ~ lol~,UOD
- 88 Z 0 01 Sl _ 58 - - ~ - L6 8-0 - - - 001 ~ 1~
~v- LZ81~1 ~ 6'01 L01 1 01 01 0 0~ 0 01 S LZ 1~ LZI ~01 O~ZI 01 Sl 0~ 5~ 6 8 0?06L ~ L- 6 ~01 5 ' L 01 0 08 0~ 8 SlIvl~ 1 ~ 6 ~OT 6 5 Ol 5I Q 55 L
S'81ZLL 08 Z01 l l 01 0~ OZ 05 9 651 ZSL 8 ZL 501 Z9 J;Ji 51 OZ 59 5 Z91 Z16 5 ~'8 ZOI 1~ S Sl OZ 59 - - 101 8-~ Z 51 OZ 59 Fsd~~sd~ % ~ 0oul/ ql ~ %~ au~lodo~ ~aq~
P(X~ ~ed~ UF ~ leuol~un,~ sselg ~S x~
(Z~Xal~ tZ)~ [ (z)~~z)n (Z)~ (z)pOZ ~1)~ %-~M 'PUala * pual~ eu~ u~ /~aqF~ sselo/~
I a 080l92-M 10 -It will be apparent from the physical proper~y da~a presented in Table I that SA~ is a brittle, low impact resin which is not substan-tially improved by the addition of either glass fiber or functional copolymer alone, as shown by the data for Control Blends A-C. The combina-tion of SAN, a functional copolymer containing as little as 2 wto ~ IBMA functional monomer units and ~lass fiber results in a composition exhibiting a marked improvement in impact properties (Compare Example 3 with Controls B
and C). Further increases in the IBMA content of the functional copolymer, Examples 4 and 5~
impart additional increases in impact and heat deflection temperature values for compositions comprising a single level (15 wt.%) of function-al copolymer, - For compositions containing a single level of glass, an increase in the amount of functional copolymer generally results in improved impact and/or heat def lection properties ( compare Example 5 with 6, Example 7 with 8 and Example g with 10) without markedly affecting the rigidity of the blends, The level of glass fiber in SAN compositions may thus be 25 increased to produce increasingly rigid compo sites while maintaining desirable impact and heat deflection values (Compare Examples 5 ~ 7 and 9 and Examples 6~ 8 and lO).
Examples 11-14~
In the following Examples, summarized in Table II~ blends containing various levels of SAN, 1/4" chopped glass fiber and SAN-IBMA
functional copolymer were prepared by dry-mi~ing the components in a PK blender for five minutes and then inje~tion molding the powdered mixture on a 1 oz. Battenfeld screw in~ection molding machine havinq a 2.5:1 compression ratio, at a stock temperature of 430F, and at minimum back pressure ~0-50 psi) to provide test specimensO
P~Pla~ u~F~a.cuF ale saldwes ~ ~
'I al~eL ~aS (Z) aaS Ola~~ e~~ ul ~ %'~M (I) :Sa~oN
~-6~ 8~6 I'll 66 60 ~ ~ ~Z 08 a lol~,uo~
1-9!, Z55 ~ 8-S L6 1-0 - O O 001 ~ 10 L OZ 866 ~ 0 Zl Z01 1 8 01 51 OZ Sg ~T
681 8~S ~ O-L 96 Z'O 01 51 0 58 ~1 O'IZ 696 5 ~'ZI Zûl 6' S Sl OZ S9 Zl S'PI LS ~9-L S6 Z-O S Sl 0 S8 11 ISCI~19d~ 9~ FS~ ~UF/ ql ~ %~ qt~ GN I
l~.S P~ UF ) leu~F~u~ sse~ ~ ~
~xa~z)xal~ (z~ ~z)n (z)~H(z) (1) %-'~M 'pua ,;spuala.~ el!~OF~;~U~ /$æiT~!I ssel9/~
II alqe~
080192~M - 13 -The property data fsr the in~ection molded compositions summarized in Table II more clearly demonstrate the enhancPment of proper-ties produced by incorporatiny ~he functional copolymer into glass fiber reinforced SAN
blends~ The addition of 1/4" chopped glass fiber alone to the SAN resin of Control A
results in a very rigid but quite brittle composite ~Control B). The combination of SAN-IBMA functional copolymer alone with an SAN
resin lowers the hea~ def lection emperature values for SAN resin without improving other properties (compare Examples 71 and 13 with Control A). Combinations comprising S~N, glass fiber and functionai copolymer exhibit a marked and desirable enhancement of impact properties, neat distortion values and ductility (E~ while maintaining the rigidity characteristic of SAN-glass fiber composites tcompare Examples 12 and 14 with Examples 11, 13 and Control D).
Examples 15-30~
The use of functional copolymers improves the properties of glass fiber rein-forced thermoplastic resins other than SAN. In the followin~ Examples, set forth in Table IIIv a variety of glass fiber reinforced thermoplas-tic resins were compounded with functional copolymers by milling and compression molding the blends substantially as described for Examples 3-10.
The functional co~olymers employed in these Examples were prepared as in Example 1~
but employing the indicated ethylenically-unsa-turated monomer and functional monomersS
1 ~Iqe,L 'z a~ o .~P~ ~n-"~YOl~ST, ~:I !a~,e~a~ I~PF;~15 = ~ (Z~
apFxo aua~ od pue S~H ~o pualq = oaa~ 'a~l~e~~
a~~e-au~sl~au~ d~ adC~ 3PF~P~
-aua~s =~;W~ '~la ~$~F ~6F~1 paF~Fpa~~ u %o~ - SaIE~ ~aua~ s~l~ = au~s d ~ s~
-9~ 869 g O~L 86 8-0 ~I~5 51 OZ 59oad~a 0 Z ~ ZS S 5 g ~8 Z ~ - O OZ 08 C~ Z
9 Zl LIL 8 8 S 'P6 8~0 ~I-~ 51 OZ 59 ~wa 8Z
Z 8~ I,lL ~ L S 06 9-0 - O OZ 59 ~ LZ
Z81 9~ 5 5 01 LO~ L S Wl~ 51 OZ SS ~S 9z 8 l I ~ Z ~aI-~s~ 51 OZ 59 ~dSl~d~ sz - - - - SL L 8~ ~S 51 OZ 59 ~dS~ ~Z ~, - - - - Z i 1 6 0 - O 0~ 08 ~S~ Z ~, O - Z91 IOL 8 Z 9 ~ l l 9 5 ~I-~dS 51 OZ 59 ~--S ZZ
~Z~ 8ZL ~ 3,-L Z6 5 5 - 51 - OZ S9 ~; IZ
5 8I L~L - 1 9 ~6 5 8 ~3-N~ 51 OZ 59 saIH OZ
9I ZI L ~ S 9 L6 5 8 ~I-~S Sl OZ 59 SaIH 61 i Z L 809 8 5 ~ Z6 5 5 - O OZ 08 SaIH 81 8 ZI 8ZL 8 5 LL 5 ~I~ 51 ûZ 59 3u~$~ Ll 1-~1 99L Z 5 5 8~ 8- ~S Sl OZ 59 ~U~Sd 91 Oi g~g ~ ~- 88 L Z - O OZ 08 ~ua~gd51 FS~2I % FSd~ ~0 ~IF/-ql-~ clF~%-~M ~ N
~;~ed~r (Z) leuoF~un~ sselg x~
X3~ Xa~ (~ I)PZTl~u~F~un~ %~M 'pual~ u~sa~
spua~a l~~lcd ~ leuo~un~ Sselg/~Fsa~d ~F~seldouL~a eL
080192-M - 15 ~
The addition of functional copolymers to a variety of glass fiber rei.nforced thermo-plastic monovinylidene resins enhances the impact, ductility and heat distortion tempera-ture proper~ies of the compositesr as shown by the ~xamples in Table I~I~ Glass fiber filled polystyrene, Example 15, is a brittle composite without the incorporation of styrene-I~MA or styrene-glycidyl methacrylate copolymer, as shown by the compositions of ~xamples 16 and 17. ~urprisingly, even thou~h styrene maleic anhydride copolymer is a functiollal copolymert a composition comprising styrene-maleic anhydride copolymer (S-MA) and glass fiber (Example 213l exhibits further property enhancement with the addition of a styrene-acrylonitrile-IBMA func-tional copolymer. The principle is readily extended to other ~lass fiber reinforced resins including high impact polystyrene, Examples 18~20, alpha methylstyrene-acrylonitrile high heat resins, Examples 23~25, polymethyl methyl-methacrylate, Examples 27-28 and to HIPS -polyphenylene ether blends, Examples 29-30.
As is well known in the processing art, the physical properties and particularly the impact properties of thermoplastic resins may vary over a wide range depending upon the compounding conditions employed. For example~
as will be se~n from an examination of the data 30 for the compression molded composition of example 5 (Table X) and the iniection molded composition of Example 14 (Table II3, many of the physical property values of otherwise identical compositions depend upon the method u~ed for their processing~ In processing glass-filled thermoplastic resins, conditions which affect the uniformity of fiber dispersion in the matrix resin are also known ~o markedly change the impact properties of molded articles, as does processing which increases the amount of fiber breakage. In general, it has been thought that good fiber dispersion is necessary to attaining good reinforcement, while fiber breakaye is thought to reduce impact properties.
Glass fiber used for reinforcing thermoplastics is usually obtained by chopping or milling fiber glass strand to produce di-screte fiber bundles of substantially uniform length and made up of many individual glass fibers. Melt processing thermoplastic resins containing chopped fiber under high shear conditions as in a conven~ional compounding extruder can be used to disperse the fibers but normally severe fiber damage occurs. Consider-able efort, therefore, has gone into develop.ing methods for "openin~ up" the bundles (i,e., separating the bundles into individual fibers) and uniformly dispersing the fibers in the thermoplastic matrix with minimimum damage to the fibers. Compositions produced by these processes are generally thought to be better reinforced and are more uniform in appearance~
As will be seen from the followin~ Example~
the compositions of this invention surprisingly exhibit better impact properties when processed under conditions which resu.lt in less-than-uni-form fiber dispersion.
Example 31. A composition containing 65 parts SAN, 20 parts 1/4" glass fiber and 15 parts SAN-IBMA functional copolymer (10% IBMA) was prepared as in Example 14 by ~ry-blendin~
the glass f iber and powdered resins in a PK
blender for five minutes. The fiber-resin blend was injection molded on a 1 OZr Battenfeld screw injection molding machine having a 2.5:1 com-pression ratio and at a stock temperature of 430F, and using controlled back pressures in the range 0-600 p5i, to provide test specimens.
The variation of impact properties and fiber dispersion with molding back pressure is summa-rized in Table IV, below.
A control composition, Control E, containing 80 parts SAN resln and 20 parts 1/4"
glass fiber was prepared and molded in substan-tially the same way to provide test specimens~or comparison purposes, FSd 05 ~ P~llol~uo~ 'palnse~ul se (~
uo~enle~a lensFA ( z ~ I
'sleq .,8/~ ou uF/ q~ edwF PozI ( I ) :sa~N 3:
s~lpunq ~ax~slp 6-0 -~ Fsd 05~0 sdulnl~ laqT~ ~ o ~ ~ z FSd OOl pas~adslp~ M 6- 0 ~ ~ Fsd ~Q~
w~o~Fun 6- 0 L 0 FSd 003 (Z)uoFs~dsFa ( ~ ed~ e~ I alnssa~
;~ ~ g ~Idul~x~
~o aaOld l~d~I po~I uo suoF~Ipuo ~ ~uFplob~ ~o ~3a~
080192-M ~ 19 -As will be seen from ~he data in Table IV, increasing the back pressure improves the iEiber dispersion, but I~od impact values are sharply decreased. A~ ~he lowest control pressuret 50 psi, the fiber qlass bundles were not opened up or fully separated into individual fibers. The molded spe~imen was visually non-uniform and contained clumps of glass fiber distributed throughout. As is well known~
increasing back pressure results in lowered resin through-put and in increased shear mixing which acts to improve fiber dispersion but also results in greater fiber breakage. As expected, fiber dispersion improves with in~reased back pressure, giving a visually uniform dispersion of fiber in the matrix resin at the highest back pressure (600 psi). Surprisingly, for the composi~ion of this invention, Example 31, the low back pressure produced moldings having poor fiber dispersion which exhibited very much greater impact properties. The Control E
example, which does not contain functional copolymer according to the teaching of ~his invention, exhibited substantially equivalen~
~5 impact at all degrees of fiber dispersion. The effective back pressure range for good impact properties will be seen to lie in the range of from 0 to about 100 psiy and preferably from about 0 to about S0 psi.
The improved method of this invention thus permits at~aining high impact properties in glass-filled monovinylidene resins without requirin~ process steps designed to maximize disper~ion of the fiber in the matrix resin.
The minimal shear conditions employed in this process permit reprocessing of the ~lass-filled resin without loss in impact properties and thus allows the re-use of scrap, a desirable and economically advantageous result. Althou~h the principles of this process wi71 be applicable to most thermal processing methods commonly employ-ed with glas~-filled thermoplastic resins, the greatest advantages will lie in use wi~h screw-fed means for melt processing resin~ such as forexample screw-fed injection molding machines and machines for melt extrusing resins such as tho~e used in the prod~ction of extruded ~heet and profile. The use of low back pressures ha~ the further advantage of allowing more rapid through-put of resin thus increasing production rates.
The invention will thus be seen to be an improved glass fiber reinforced thermoplastic resin composition comprising a thermoplastic monovinylidene resin, glass fiber, and a func-tional copolymer of at least one ethylenically unsaturated monomer and a copolymerizable functional monomer, and a method ~or enhancing the impact and ductility characteristics of glas~ fiber reinforced thermoplastic resins.
A polymerization kettle was charged with 81 g. of deionized wa~er, 0.06 9. of sodium dodecylbenzene sulfonate (23%) suractant and 0.23 g. of sodium carbonate. The charge was blanketed with ni~rogen, stirred and heated to 65 C. A monomer emulsion containing 81 9. of deionized water, 62.7 9. of styrene, 27.3 g. of acrylonitrile, 10.0 g. of N-isobutoxymethyl-acrylamide and 1.92 g. of the dioctyl ester of sodium sulfosuccinic acid was prepared by stirring the surfactant into the water, then adding the monomer.s slowly and with strong stirring. An initial char~e of 2.11 gO of the monomer emulsion was added to the kettle ollow-ed by a solution of 0035 g. of sodium persulfate in 3.85 9 of water as the initiator. The stirred mixture was heated at 65CC for 20 minO, then 0.5 g. of t dodecyl mercaptan (molecular weight regulator) were addedO The remaining monomer emulsion was then continuously added to the kettle over a three hour period while maintaining the nitrogen blanket and continua].ly heating and stirring the mixture at 65Co At the end of the addition of the monomer emulsion, the mixture was heated at 65C for an additional hour to complete the polymerization~ After cooling~ the polymer was collected by coa~ula-tion in three volumes of aqueous aluminumsulfate at 140F, filtering and washing the 6~3 080192-M ~ 7 -coagulated resin with water to remove surfac-tant~ The resin, amounting to ~8 g~ after dryiny, was a copolymer containing 6207%
wt.% styrene units, 27~3 wt.% acrylonitrile units and 10 wt.% M-isobutoxymethyl acrylamide unit~D
Example 20 Blends of Glass ~iber~
Thermoplastic Resin and Functional Copolymer.
A blend consisting of ~5 g. of granu lated ~tyrene-acrylonitrile resin~ obtained from Dow as Tyril*860, 20 9. of 1/4" chopped glass fiber, obtained from Owens Corning as B85 EB, and 15 9~ of powdered functional copolymer (see .Example 1) was prepared by dry-mixing the powdered resins and glass fiber.. The mixture was injection molded to provide test specimens.
The test ~pecimen exhibited a room temperature Xzod impact of 203 ft. lbs,~in. notch an~ a heat defle~tion temperature ~10 mil~ ~f 219~.
An injec~ion molded contrsl blend containing no funct~onal copolymer, prepared from ~0 ~0 of granulated styrene acrylonitrile resin and 20 gO of chopped 1/~" qlass fibert had an Izod impact of 1.0 ~t~ lbs./inO notch and a heat deflection temperature (10 mil~ of 212F~
It will thus be apparent from these data that the incorporation of 15 wt.~ of functional copolymer into ~ glass-filled sty-rene-acrylonitril~ resin provides a subs~antial improvement in impact properties and heat deflection temperature, , *trade mark Example 3 - 10~
In the followirlg Examples j, summarized in Table 1, functional copolymers containing from 2 to 10 wt. P6 N-isobutoxyme~hyl acrylamide 5 (IBMA) functional monomer uni~s and correspons3-ingly from 98 lto 90 wt. % styrene and acryloni-ltrile monomer units in a 2 0 3 :1 ratio were prepared substantially by the process of Example 19 then blended with styrene-acryloni-10 triie resin (Tyril 860) and 1/4'J chopped glass~Eiber ~ 885EB~ by milling on a two roll mill at 420F iEor 5 min.. The blend was sheeted-c:~u~, coo~ ed and then compression molded a~c 365~ F for 6 min. to form test spe~imens. The physi-~al 15 property data for the blends is reflected in Table I.
Control blends were prepare~l Iby milling and molding as for the specimens of Examples 3-10., ~~ * trade mark pa~loul UOISS~ldiL~ al~ S~ S
Sleq .8/1 pa~ 1~ ~edu}r P~ZI
'am~e~ uoF~a~IFQI 01 ~FSd ~SZ = La~ e~ep ~,s~ a~n~e~adi~3~ Ul~d (Z) odc~
L~ 0 WF~El~d~d 10~ d~x;~ pFulel~e ~ olnqosl-N ~ ~I (1) :5~ N
-ZI 866 I'll 66 6 0 - - OZ 08 ~ lol~,UOD
- 88 Z 0 01 Sl _ 58 - - ~ - L6 8-0 - - - 001 ~ 1~
~v- LZ81~1 ~ 6'01 L01 1 01 01 0 0~ 0 01 S LZ 1~ LZI ~01 O~ZI 01 Sl 0~ 5~ 6 8 0?06L ~ L- 6 ~01 5 ' L 01 0 08 0~ 8 SlIvl~ 1 ~ 6 ~OT 6 5 Ol 5I Q 55 L
S'81ZLL 08 Z01 l l 01 0~ OZ 05 9 651 ZSL 8 ZL 501 Z9 J;Ji 51 OZ 59 5 Z91 Z16 5 ~'8 ZOI 1~ S Sl OZ 59 - - 101 8-~ Z 51 OZ 59 Fsd~~sd~ % ~ 0oul/ ql ~ %~ au~lodo~ ~aq~
P(X~ ~ed~ UF ~ leuol~un,~ sselg ~S x~
(Z~Xal~ tZ)~ [ (z)~~z)n (Z)~ (z)pOZ ~1)~ %-~M 'PUala * pual~ eu~ u~ /~aqF~ sselo/~
I a 080l92-M 10 -It will be apparent from the physical proper~y da~a presented in Table I that SA~ is a brittle, low impact resin which is not substan-tially improved by the addition of either glass fiber or functional copolymer alone, as shown by the data for Control Blends A-C. The combina-tion of SAN, a functional copolymer containing as little as 2 wto ~ IBMA functional monomer units and ~lass fiber results in a composition exhibiting a marked improvement in impact properties (Compare Example 3 with Controls B
and C). Further increases in the IBMA content of the functional copolymer, Examples 4 and 5~
impart additional increases in impact and heat deflection temperature values for compositions comprising a single level (15 wt.%) of function-al copolymer, - For compositions containing a single level of glass, an increase in the amount of functional copolymer generally results in improved impact and/or heat def lection properties ( compare Example 5 with 6, Example 7 with 8 and Example g with 10) without markedly affecting the rigidity of the blends, The level of glass fiber in SAN compositions may thus be 25 increased to produce increasingly rigid compo sites while maintaining desirable impact and heat deflection values (Compare Examples 5 ~ 7 and 9 and Examples 6~ 8 and lO).
Examples 11-14~
In the following Examples, summarized in Table II~ blends containing various levels of SAN, 1/4" chopped glass fiber and SAN-IBMA
functional copolymer were prepared by dry-mi~ing the components in a PK blender for five minutes and then inje~tion molding the powdered mixture on a 1 oz. Battenfeld screw in~ection molding machine havinq a 2.5:1 compression ratio, at a stock temperature of 430F, and at minimum back pressure ~0-50 psi) to provide test specimensO
P~Pla~ u~F~a.cuF ale saldwes ~ ~
'I al~eL ~aS (Z) aaS Ola~~ e~~ ul ~ %'~M (I) :Sa~oN
~-6~ 8~6 I'll 66 60 ~ ~ ~Z 08 a lol~,uo~
1-9!, Z55 ~ 8-S L6 1-0 - O O 001 ~ 10 L OZ 866 ~ 0 Zl Z01 1 8 01 51 OZ Sg ~T
681 8~S ~ O-L 96 Z'O 01 51 0 58 ~1 O'IZ 696 5 ~'ZI Zûl 6' S Sl OZ S9 Zl S'PI LS ~9-L S6 Z-O S Sl 0 S8 11 ISCI~19d~ 9~ FS~ ~UF/ ql ~ %~ qt~ GN I
l~.S P~ UF ) leu~F~u~ sse~ ~ ~
~xa~z)xal~ (z~ ~z)n (z)~H(z) (1) %-'~M 'pua ,;spuala.~ el!~OF~;~U~ /$æiT~!I ssel9/~
II alqe~
080192~M - 13 -The property data fsr the in~ection molded compositions summarized in Table II more clearly demonstrate the enhancPment of proper-ties produced by incorporatiny ~he functional copolymer into glass fiber reinforced SAN
blends~ The addition of 1/4" chopped glass fiber alone to the SAN resin of Control A
results in a very rigid but quite brittle composite ~Control B). The combination of SAN-IBMA functional copolymer alone with an SAN
resin lowers the hea~ def lection emperature values for SAN resin without improving other properties (compare Examples 71 and 13 with Control A). Combinations comprising S~N, glass fiber and functionai copolymer exhibit a marked and desirable enhancement of impact properties, neat distortion values and ductility (E~ while maintaining the rigidity characteristic of SAN-glass fiber composites tcompare Examples 12 and 14 with Examples 11, 13 and Control D).
Examples 15-30~
The use of functional copolymers improves the properties of glass fiber rein-forced thermoplastic resins other than SAN. In the followin~ Examples, set forth in Table IIIv a variety of glass fiber reinforced thermoplas-tic resins were compounded with functional copolymers by milling and compression molding the blends substantially as described for Examples 3-10.
The functional co~olymers employed in these Examples were prepared as in Example 1~
but employing the indicated ethylenically-unsa-turated monomer and functional monomersS
1 ~Iqe,L 'z a~ o .~P~ ~n-"~YOl~ST, ~:I !a~,e~a~ I~PF;~15 = ~ (Z~
apFxo aua~ od pue S~H ~o pualq = oaa~ 'a~l~e~~
a~~e-au~sl~au~ d~ adC~ 3PF~P~
-aua~s =~;W~ '~la ~$~F ~6F~1 paF~Fpa~~ u %o~ - SaIE~ ~aua~ s~l~ = au~s d ~ s~
-9~ 869 g O~L 86 8-0 ~I~5 51 OZ 59oad~a 0 Z ~ ZS S 5 g ~8 Z ~ - O OZ 08 C~ Z
9 Zl LIL 8 8 S 'P6 8~0 ~I-~ 51 OZ 59 ~wa 8Z
Z 8~ I,lL ~ L S 06 9-0 - O OZ 59 ~ LZ
Z81 9~ 5 5 01 LO~ L S Wl~ 51 OZ SS ~S 9z 8 l I ~ Z ~aI-~s~ 51 OZ 59 ~dSl~d~ sz - - - - SL L 8~ ~S 51 OZ 59 ~dS~ ~Z ~, - - - - Z i 1 6 0 - O 0~ 08 ~S~ Z ~, O - Z91 IOL 8 Z 9 ~ l l 9 5 ~I-~dS 51 OZ 59 ~--S ZZ
~Z~ 8ZL ~ 3,-L Z6 5 5 - 51 - OZ S9 ~; IZ
5 8I L~L - 1 9 ~6 5 8 ~3-N~ 51 OZ 59 saIH OZ
9I ZI L ~ S 9 L6 5 8 ~I-~S Sl OZ 59 SaIH 61 i Z L 809 8 5 ~ Z6 5 5 - O OZ 08 SaIH 81 8 ZI 8ZL 8 5 LL 5 ~I~ 51 ûZ 59 3u~$~ Ll 1-~1 99L Z 5 5 8~ 8- ~S Sl OZ 59 ~U~Sd 91 Oi g~g ~ ~- 88 L Z - O OZ 08 ~ua~gd51 FS~2I % FSd~ ~0 ~IF/-ql-~ clF~%-~M ~ N
~;~ed~r (Z) leuoF~un~ sselg x~
X3~ Xa~ (~ I)PZTl~u~F~un~ %~M 'pual~ u~sa~
spua~a l~~lcd ~ leuo~un~ Sselg/~Fsa~d ~F~seldouL~a eL
080192-M - 15 ~
The addition of functional copolymers to a variety of glass fiber rei.nforced thermo-plastic monovinylidene resins enhances the impact, ductility and heat distortion tempera-ture proper~ies of the compositesr as shown by the ~xamples in Table I~I~ Glass fiber filled polystyrene, Example 15, is a brittle composite without the incorporation of styrene-I~MA or styrene-glycidyl methacrylate copolymer, as shown by the compositions of ~xamples 16 and 17. ~urprisingly, even thou~h styrene maleic anhydride copolymer is a functiollal copolymert a composition comprising styrene-maleic anhydride copolymer (S-MA) and glass fiber (Example 213l exhibits further property enhancement with the addition of a styrene-acrylonitrile-IBMA func-tional copolymer. The principle is readily extended to other ~lass fiber reinforced resins including high impact polystyrene, Examples 18~20, alpha methylstyrene-acrylonitrile high heat resins, Examples 23~25, polymethyl methyl-methacrylate, Examples 27-28 and to HIPS -polyphenylene ether blends, Examples 29-30.
As is well known in the processing art, the physical properties and particularly the impact properties of thermoplastic resins may vary over a wide range depending upon the compounding conditions employed. For example~
as will be se~n from an examination of the data 30 for the compression molded composition of example 5 (Table X) and the iniection molded composition of Example 14 (Table II3, many of the physical property values of otherwise identical compositions depend upon the method u~ed for their processing~ In processing glass-filled thermoplastic resins, conditions which affect the uniformity of fiber dispersion in the matrix resin are also known ~o markedly change the impact properties of molded articles, as does processing which increases the amount of fiber breakage. In general, it has been thought that good fiber dispersion is necessary to attaining good reinforcement, while fiber breakaye is thought to reduce impact properties.
Glass fiber used for reinforcing thermoplastics is usually obtained by chopping or milling fiber glass strand to produce di-screte fiber bundles of substantially uniform length and made up of many individual glass fibers. Melt processing thermoplastic resins containing chopped fiber under high shear conditions as in a conven~ional compounding extruder can be used to disperse the fibers but normally severe fiber damage occurs. Consider-able efort, therefore, has gone into develop.ing methods for "openin~ up" the bundles (i,e., separating the bundles into individual fibers) and uniformly dispersing the fibers in the thermoplastic matrix with minimimum damage to the fibers. Compositions produced by these processes are generally thought to be better reinforced and are more uniform in appearance~
As will be seen from the followin~ Example~
the compositions of this invention surprisingly exhibit better impact properties when processed under conditions which resu.lt in less-than-uni-form fiber dispersion.
Example 31. A composition containing 65 parts SAN, 20 parts 1/4" glass fiber and 15 parts SAN-IBMA functional copolymer (10% IBMA) was prepared as in Example 14 by ~ry-blendin~
the glass f iber and powdered resins in a PK
blender for five minutes. The fiber-resin blend was injection molded on a 1 OZr Battenfeld screw injection molding machine having a 2.5:1 com-pression ratio and at a stock temperature of 430F, and using controlled back pressures in the range 0-600 p5i, to provide test specimens.
The variation of impact properties and fiber dispersion with molding back pressure is summa-rized in Table IV, below.
A control composition, Control E, containing 80 parts SAN resln and 20 parts 1/4"
glass fiber was prepared and molded in substan-tially the same way to provide test specimens~or comparison purposes, FSd 05 ~ P~llol~uo~ 'palnse~ul se (~
uo~enle~a lensFA ( z ~ I
'sleq .,8/~ ou uF/ q~ edwF PozI ( I ) :sa~N 3:
s~lpunq ~ax~slp 6-0 -~ Fsd 05~0 sdulnl~ laqT~ ~ o ~ ~ z FSd OOl pas~adslp~ M 6- 0 ~ ~ Fsd ~Q~
w~o~Fun 6- 0 L 0 FSd 003 (Z)uoFs~dsFa ( ~ ed~ e~ I alnssa~
;~ ~ g ~Idul~x~
~o aaOld l~d~I po~I uo suoF~Ipuo ~ ~uFplob~ ~o ~3a~
080192-M ~ 19 -As will be seen from ~he data in Table IV, increasing the back pressure improves the iEiber dispersion, but I~od impact values are sharply decreased. A~ ~he lowest control pressuret 50 psi, the fiber qlass bundles were not opened up or fully separated into individual fibers. The molded spe~imen was visually non-uniform and contained clumps of glass fiber distributed throughout. As is well known~
increasing back pressure results in lowered resin through-put and in increased shear mixing which acts to improve fiber dispersion but also results in greater fiber breakage. As expected, fiber dispersion improves with in~reased back pressure, giving a visually uniform dispersion of fiber in the matrix resin at the highest back pressure (600 psi). Surprisingly, for the composi~ion of this invention, Example 31, the low back pressure produced moldings having poor fiber dispersion which exhibited very much greater impact properties. The Control E
example, which does not contain functional copolymer according to the teaching of ~his invention, exhibited substantially equivalen~
~5 impact at all degrees of fiber dispersion. The effective back pressure range for good impact properties will be seen to lie in the range of from 0 to about 100 psiy and preferably from about 0 to about S0 psi.
The improved method of this invention thus permits at~aining high impact properties in glass-filled monovinylidene resins without requirin~ process steps designed to maximize disper~ion of the fiber in the matrix resin.
The minimal shear conditions employed in this process permit reprocessing of the ~lass-filled resin without loss in impact properties and thus allows the re-use of scrap, a desirable and economically advantageous result. Althou~h the principles of this process wi71 be applicable to most thermal processing methods commonly employ-ed with glas~-filled thermoplastic resins, the greatest advantages will lie in use wi~h screw-fed means for melt processing resin~ such as forexample screw-fed injection molding machines and machines for melt extrusing resins such as tho~e used in the prod~ction of extruded ~heet and profile. The use of low back pressures ha~ the further advantage of allowing more rapid through-put of resin thus increasing production rates.
The invention will thus be seen to be an improved glass fiber reinforced thermoplastic resin composition comprising a thermoplastic monovinylidene resin, glass fiber, and a func-tional copolymer of at least one ethylenically unsaturated monomer and a copolymerizable functional monomer, and a method ~or enhancing the impact and ductility characteristics of glas~ fiber reinforced thermoplastic resins.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition comprising:
(a) from 95 to 50 wt.% of a blend of a rigid thermoplastic monovinylidene resin selected from the group consisting of styrenic resins and acrylic resins; and a copolymer of at least one monovinylidene mono-mer selected from the group consisting of monovinyl aromatic compounds, acrylic compounds, and methacrylic-compounds and from 1 to 20 wt.% of at least one ethylenically-unsaturated monomer containing at least one functional radical selected from the group consisting of carbonyl radicals and epoxy radicals; and (b) from 5 to 50 wt.% of a glass reinforcing fiber.
(a) from 95 to 50 wt.% of a blend of a rigid thermoplastic monovinylidene resin selected from the group consisting of styrenic resins and acrylic resins; and a copolymer of at least one monovinylidene mono-mer selected from the group consisting of monovinyl aromatic compounds, acrylic compounds, and methacrylic-compounds and from 1 to 20 wt.% of at least one ethylenically-unsaturated monomer containing at least one functional radical selected from the group consisting of carbonyl radicals and epoxy radicals; and (b) from 5 to 50 wt.% of a glass reinforcing fiber.
2. The composition of claim 1 wherein said carbonyl radicals are selected from the group consisting of carboxylic acid, carboxylic anhydride and amide.
3. A composition comprising:
(a) from 95 to 50 wt.% of a blend of a rigid thermoplastic monovinylidene resin selected from the group consisting of styrenic resins and acrylic resins;
a copolymer of at least one monovinylidene mono-mer selected from the group consisting of monovinyl aromatic compounds, acrylic compounds and methacrylic compounds and from 1 to 20 wt.% of a monomer selected from the group con-sisting of maleic anhydride, glycidyl methacrylate and N-alkoxymethyl acrylamide; and (b) from 5 to 50 wt.% of a glass reinforcing fiber.
(a) from 95 to 50 wt.% of a blend of a rigid thermoplastic monovinylidene resin selected from the group consisting of styrenic resins and acrylic resins;
a copolymer of at least one monovinylidene mono-mer selected from the group consisting of monovinyl aromatic compounds, acrylic compounds and methacrylic compounds and from 1 to 20 wt.% of a monomer selected from the group con-sisting of maleic anhydride, glycidyl methacrylate and N-alkoxymethyl acrylamide; and (b) from 5 to 50 wt.% of a glass reinforcing fiber.
4. The composition of claim 3 wherein the monovinylidene resin is a styrenic resin selected from the group consisting of polystyrene, styrene-acrylonitrile co-polymers, styrene-alpha methylstyrene-acrylonitille copolymers, styrene-methyl methacrylate copolymers, styrene-maleic anhydride copolymers, and high impact polystyrene.
5. The composition of claim 3 wherein said monovinylidene resin is polymethyl methacrylate.
6. The composition of claim 3 further comprising a non-styrenic thermoplastic resin.
7. The composition of claim 3 further com-prising polyphenylene ether.
8. In a blend composition comprising from 95 to 50 wt.% of a rigid thermoplastic monovinylidene resin selected from the group consisting of styrenic resins and acrylic resins and correspondingly from 5 to 50 wt.% of a glass reinforcing fiber, the improvement wherein said blend composition further comprises a copolymer of from 99 to 80 parts by weight of at least one monovinylidene monomer selected from the group consisting of monovinylaromatic compounds, acrylic compounds and methacrylic compounds and correspondingly from 1 to 20 parts by weight of a monomer selected from the group consisting of maleic anhydride, glycidyl methacrylate and N alkoxymethyl acrylamide, said monovinylidene resin and said copolymer being present in a weight ratio of from about 4.33 to about 1/1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/328,159 US4414342A (en) | 1981-12-07 | 1981-12-07 | Glass-filled thermoplastic resins |
| US328,159 | 1981-12-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196123A true CA1196123A (en) | 1985-10-29 |
Family
ID=23279768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000414195A Expired CA1196123A (en) | 1981-12-07 | 1982-10-26 | Glass-filled thermoplastic resins |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4414342A (en) |
| EP (1) | EP0081230A1 (en) |
| JP (1) | JPS58104950A (en) |
| CA (1) | CA1196123A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3741670A1 (en) * | 1987-12-09 | 1989-06-22 | Basf Ag | REINFORCED THERMOPLASTIC MOLDS BASED ON POLYPHENYLENE ETHER |
| JPH02258855A (en) * | 1989-03-31 | 1990-10-19 | Idemitsu Kosan Co Ltd | Surface-treated inorganic filler and styrene resin composition |
| US5270353A (en) * | 1989-02-10 | 1993-12-14 | Idemitsu Kosan Co., Ltd. | Resin composition |
| DE19621734A1 (en) * | 1996-05-30 | 1997-12-04 | Basf Ag | Flame-retardant thermoplastic molding compounds based on polyphenylene ethers |
| FR2885316B1 (en) * | 2005-05-04 | 2007-08-31 | Saint Gobain Vetrotex | PROCESS FOR MANUFACTURING A COMPOSITE WORKPIECE FROM HIGH GLASS DENSITY GRANULES |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3414432A (en) * | 1965-10-04 | 1968-12-03 | Exxon Research Engineering Co | Sizing glass fibers with polybutadienedicarboxylic acid anhydride amino salt adducts |
| US3619229A (en) * | 1968-09-05 | 1971-11-09 | Dow Corning | Reinforced polystyrene and its copolymers |
| GB1363304A (en) * | 1970-07-30 | 1974-08-14 | Sumitomo Chemical Co | Polyolefin compositions |
| US3804919A (en) * | 1972-04-20 | 1974-04-16 | Dart Ind Inc | Synergistic blends of modified polyolefins and unmodified polyolefins |
| JPS5118935B2 (en) * | 1972-08-07 | 1976-06-14 | ||
| US3940537A (en) * | 1973-07-12 | 1976-02-24 | Ici United States Inc. | Fibrous mats |
| JPS54125263A (en) * | 1978-03-22 | 1979-09-28 | Nitto Boseki Co Ltd | Production of formed plate of fiberglass reinforces resin |
| US4212697A (en) * | 1976-09-22 | 1980-07-15 | Nitto Boseki Co., Ltd. | Process for producing glass fiber-reinforced resin molded sheets |
| JPS5531822A (en) * | 1978-08-24 | 1980-03-06 | Sumitomo Chem Co Ltd | Manufacture of glassfiber-reinforced transparent resin plate |
| JPS5831822A (en) * | 1981-08-13 | 1983-02-24 | Toshiba Corp | Separator for magnetic members |
-
1981
- 1981-12-07 US US06/328,159 patent/US4414342A/en not_active Expired - Fee Related
-
1982
- 1982-10-26 CA CA000414195A patent/CA1196123A/en not_active Expired
- 1982-12-02 JP JP57212068A patent/JPS58104950A/en active Granted
- 1982-12-06 EP EP82111296A patent/EP0081230A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0378427B2 (en) | 1991-12-13 |
| JPS58104950A (en) | 1983-06-22 |
| US4414342A (en) | 1983-11-08 |
| EP0081230A1 (en) | 1983-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4421892A (en) | Thermoplastic polymeric material and method for the preparation thereof | |
| US4390657A (en) | Composition of polycarbonate, an ABS resin and an acrylate-methacrylate interpolymer | |
| US4503183A (en) | Polycarbonate resin molding composition | |
| CA2033320C (en) | Thermoplastic copolymer, method for production thereof, and thermoplastic resin composition containing the copolymer | |
| DE2249870B2 (en) | Composition of a polyphenylene ether and an acrylonitrile-butadiene-styrene resin (ABS resin) modified with acrylic resin | |
| EP0412370A1 (en) | ABS mouldings with improved tensile stress | |
| KR100530567B1 (en) | Thermoplastic resin composition with good impact strength | |
| CA1196123A (en) | Glass-filled thermoplastic resins | |
| CA1196132A (en) | Impact resistant polyamide moulding compositions | |
| US5159003A (en) | Polyester-compatible alloys of polycarbonate | |
| CA2489511C (en) | Glass fiber filled thermoplastic compositions with good surface appearance | |
| US4402902A (en) | Method for molding glass-filled thermoplastic resins | |
| US5061757A (en) | High impact strength polyamide blends and method for preparation thereof | |
| US20020115748A1 (en) | Glass fiber reinforced styrenic thermoplastic composites containing an aminosilane coupling agent | |
| JPH09216993A (en) | High-density thermoplastic molding composition | |
| JPH0328463B2 (en) | ||
| CN1330703C (en) | Filled weatherable compositions having a good surface appearance | |
| US6211269B1 (en) | Glass-fiber-reinforced thermoplastic ABS compositions | |
| EP0485793B1 (en) | Reinforced ABS-moulding matters containing graft polymers incorporating tert. alkyl esters, their manufacture and application | |
| EP0518150B1 (en) | Reinforced ABS moulding compositions | |
| EP0940441A1 (en) | A vinyl aromatic/ketone polymer composition | |
| US5426149A (en) | Polymers of styrene | |
| CN1063462C (en) | Long-fiber-reinforced high-impact polystyrene resin structure and molding thereof | |
| EP0527382B1 (en) | Glass fiber reinforced ABS-compositions | |
| JP2702204B2 (en) | Automotive interior parts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |