WO1996009346A1 - Composition polymere contenant un reseau interpenetrant - Google Patents

Composition polymere contenant un reseau interpenetrant Download PDF

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Publication number
WO1996009346A1
WO1996009346A1 PCT/NO1995/000171 NO9500171W WO9609346A1 WO 1996009346 A1 WO1996009346 A1 WO 1996009346A1 NO 9500171 W NO9500171 W NO 9500171W WO 9609346 A1 WO9609346 A1 WO 9609346A1
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WIPO (PCT)
Prior art keywords
polymer
weight
composition
phenolic
matrix
Prior art date
Application number
PCT/NO1995/000171
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English (en)
Inventor
Kjetil L. BØRVE
Hans Kristian Kotlar
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Borealis A/S
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Publication date
Application filed by Borealis A/S filed Critical Borealis A/S
Priority to AU36207/95A priority Critical patent/AU3620795A/en
Publication of WO1996009346A1 publication Critical patent/WO1996009346A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to a thermoplastic polymer composition having an interpenetrating network (IPN), and a method for the production thereof. More particularly the present invention relates to a polymer composition being a polymer alloy comprising a matrix resin of polyolefin and an interpenetrating network of a crosslinked phenolic polymer evenly distributed therein. By combining polymers this way, a polymer composition having a controlled morphology and a selected profile of properties can be obtained.
  • Preferred com ⁇ ponents of the present composition comprise polypropylenes and phenolic polymers, but in principle other similar polymer resins can be also used in the present process.
  • GB 1,567,375 discloses blends of thermosetting resins and copolymers of ethylene with different comonomers.
  • the pur ⁇ pose is to obtain a blend having a small thermal deformation and thus being particularly suitable for the moulding of articles.
  • neither polypropylene nor any polymer alloy technology is used.
  • EP 416,526 discloses thermoplastic resins to which phenolformaldehyde resoles are added to reduce the shrinkage of moulded sheets during curing.
  • Polypropylene is not used as the thermoplastic resin, and compatibilizing technology is not mentioned.
  • SE 387,355 discloses polyolefin/glass composites. Neither phenolic resins nor alloy technology is mentioned.
  • GB 1,463,452 discloses polyolefins modified with ⁇ -methacryloyloxypropyl-trimethoxysilane and glycidylmethacry- lates, and intended for the use as additives in the coating of metals, paper, glass, ceramics and plastics.
  • the poly- ers are not used to achieve compatibility between polyolefins and other polymers in a melted state, and blends or alloys of polypropylene and phenolic polymers are not mentioned.
  • US 4,558,089 discloses a composition comprising a granular phenolaldehyde resin blended with either a rubbery- elastic material or a thermoplastic resin or another curable resin.
  • the phenolaldehyde resin is completely or partly cured before being blended with the thermoplastic resin in, for example, an extruder, and hence said resin is not able to form any interpenetrating network (IPN).
  • IPN interpenetrating network
  • US 4,563,379 discloses a sealing web comprising a layer of EPM and/or EPDM containing an interpenetrating net ⁇ work of phenolic resins (novolak) crosslinked with formalde ⁇ hyde or hexamethylenetetramine. This composition is included in the sealing web as an integrated part thereof and polypro ⁇ pylene is not used as a matrix.
  • EP 46285 discloses a process for the preparation of plasto-elastomeric compositions by blending EPDM with polypro ⁇ pylene or polyethylene and then crosslinking the EPDM with a phenolic polymer. The purpose is to obtain a rubber material that does not contain any chlorine. The phenolic polymer cons ⁇ titutes no individual component of the blend, and polypropy ⁇ lene is not used as a matrix.
  • EP 274899 discloses composite materials, i.e. fiber- reinforced thermosetting resins, as prepregs. To improve the mechanical properties a mixture of thermosetting and thermo ⁇ plastic resins which have, or can develop, a semi-IPN struc ⁇ ture may be used. IPN materials containing epoxy as the ther ⁇ mosetting resin and different thermoplastic resins are descri- bed. Phenolic polymers or polypropylene are not mentioned.
  • the present invention thus provides a polymer com ⁇ position having an interpenetrating network.
  • Said composition comprises a polyolefin matrix, which optionally also includes a minor amount of an ethylene-propylene-butadiene polymer gra ⁇ fted with maleic anhydride (EPDM-g-MAH), and evenly distribu ⁇ ted in said matrix a thermoplastic phenolic polymer which has been crosslinked with a crosslinking agent to a crosslinking degree from 0.5 % to 50 % in such a way that it forms an interpenetrating network throughout the matrix, said matrix constituting from 99 % to 5 % by weight of the composition and the partially crosslinked phenolic resin constituting from 1 % to 95 % by weight of the composition, the amounts of said com ⁇ ponents totalling 100 % by weight.
  • EPDM-g-MAH ethylene-propylene-butadiene polymer gra ⁇ fted with maleic anhydride
  • the invention also provides a method for producing a polymer composition having an interpenetrating network.
  • a polyolefin resin optionally containing a minor amount of an ethylene-propylene-butadiene polymer grafted with maleic anhydride (EPDM-g-MAH)
  • EPDM-g-MAH ethylene-propylene-butadiene polymer grafted with maleic anhydride
  • a phenolic polymer by continuous kneading in a mixer, preferably in an inert atmosphere, while being heated to a temperature above the melting temperature of the highest-melting component, whereupon the phenolic polymer is crosslinked to a desired crosslinking degree by the use of a crosslinking agent and a suitable catalyst, which catalyst is introduced into the mixer either together with the polyolefin resin and the phenolic polymer, or separately when these components are in a melted state, and the obtained product is cooled and granulated.
  • EPDM-g-MAH ethylene
  • Fig. 1 is a scanning electron microscope (SEM) photo ⁇ graph taken at a magnification of 2000X showing the polymer composition of the invention, which consists of polypropylene and a crosslinked phenolformaldehyde (obtained in Example 8).
  • Fig. 2 is a similar photograph of an analogous com ⁇ position where the contained phenolformaldehyde polymer is not crosslinked (Example 7) .
  • Figs. 3, 4 and 5 show impact resistance properties, determined as the total energy at break; elongation at break; and moduli of elasticity, respectively, for the compositions of the invention numbered 12 to 31 and for reference composi ⁇ tions designated "P401" and "P410".
  • Figs. 6 and 7 show variations in the modulus of elas- 5 ticity for those compositions of the invention that contain 2.5 % and 10 % by weight, respectively, of phenolformaldehyde crosslinked with hexamethylenetetramine and to which there is also added ethylene-propylene-butadiene copolymer grafted with maleic anhydride (EPDM-g-MAH).
  • EPDM-g-MAH ethylene-propylene-butadiene copolymer grafted with maleic anhydride
  • Figs. 8 and 9 correspond to Figs. 6 and 7, except that polyoxymethylene is used as a crosslinking agent.
  • Figs. 10 and 11 correspond to Figs. 6 and 7, except that paraformaldehyde is used as a crosslinking agent.
  • An object of the present invention is to provide a polymer composition
  • a polymer composition comprising a matrix resin of polyolefin in which there is evenly distributed an interpenetrating network consisting of a crosslinked phenolic polymer.
  • the polyolefin resin may be selected from the group consisting of polyethylenes of low and high density; polypro ⁇ pylene homopolymers; and copolymers of propylene with ethylene and/or butadiene.
  • the polypropylene resin is either a polypropylene homopolymer or a copolymer of propylene 5 with ethylene and/or butadiene.
  • the polypropylene resin has a melt index in the range of preferably from 0.1 to 100 g/10 min, more preferred from 0.35 to 10 g/10 min, determined according to ASTM D 1238 at 230 °C and 2.16 kg load.
  • the poly ⁇ propylene resin should preferably have a weight average mole- 0 cular weight within the range of from 10.000 to 500.000 g/mole.
  • commercially available types of polypropylene resins may be used, including those containing the types of additives normally used in commer ⁇ cially available resin types.
  • the phenolic polymer used in the method of the inven ⁇ tion is a thermoplastic copolymer obtained by the polymeriza ⁇ tion of a phenolic compound with a comonomer.
  • the phenolic compound can be phenol or a phenol derivative having the for ⁇ mula:
  • R l r R 2 and R 3 which may be identical or different from each other, can be selected independently from the group consisting of H, OH, and alkyl groups having 1-5 carbon atoms (Ci. 5 alkyl groups). Mixtures of different derivatives may also be used, also in combination with phenol.
  • a particularly pref ⁇ erred mixture comprises phenol, hydroxy phenols and methyl phenols. The ratios between the components in the mixture may be varied, depending on which properties of the final composi ⁇ tion that are desired.
  • the preferred comonomer for use in the polymerization is formaldehyde or acetone; most preferred is formaldehyde.
  • the amount of comonomer is chosen such that the molar ratio between the phenolic compound and the comonomer is within the range of from 1:0.5 to 1:0.95.
  • the polymerized phenolic polymer should have a weight average molecular weight preferably within the range of from 750 to 40,000 g/mole, more preferred from 1000 to 25,000 g/mole.
  • the thermoplastic phenolic polymer has to be cross ⁇ linked in order to achieve the desired interpenetrating net ⁇ work.
  • the crosslinking reaction may be performed by the use of a number of crosslinking agents, but typically there is used: - paraformaldehydes of various chain lengths, preferably having from 5 to 15 repeating -(CH 2 0)- units; hexamethylenetetramine, C 6 H 12 N 4 ; or polyoxy ethylene, -(CH 2 -0-CH 2 -0)-.
  • the crosslinking agent is added in an amount prefer ⁇ ably from 0.01 % to 5 % by weight, more preferred from 0.5 % to 2.5 % by weight, of the amount of phenolic polymer.
  • a preferred catalyst is selected from the group consis ⁇ ting of:
  • R 4 and R 5 which may be identical or different from each other, are selected from the group consisting of H and C ⁇ j alkyl groups, and R 6 is C ⁇ alkyl,
  • R 7 , R ⁇ and R 9 which may be identical or differen from each other, are selected from the group consisting of and C x _ 5 alkyl groups;
  • the catalyst is used in an amount preferably fro 0.01 % to 5 % by weight, more preferred from 1 to 2.5 % b weight, of the amount of the phenolic polymer.
  • the degree of crosslinking of the phenolic poly mer is typically within the range of from 0.5 to 50 %, eve though both lower and higher crosslinking degrees are possibl and are contemplated by the present invention.
  • the degree o crosslinking is equal to the amount of non-extractable pheno 5 lie polymer expressed in percent by weight of the total amoun of the phenolic polymer contained in the polymer composition.
  • the amount of phenolic polymer in the final composi tion constitutes from 1 % to 95 % by weight, and thus th polyolefin resin constitutes from 99 % to 5 % by weight, wher said components of the composition total 100 % by weight.
  • the composition compri ⁇ ses from 1 % to 90 % by weight of the phenolic polymer and from 99 % to 60 % by weight of the polyolefin resin, where s said components of the composition total 100 % by weight.
  • the indicated amounts of phenolic polymer are understood to include both crosslinked and non-crosslinked phenolic polymer as well as the amounts of crosslinking agent and catalyst re ⁇ quired in the crosslinking reaction.
  • the com- o position may contain additives, such as heat and UV stabili ⁇ zers, antistatic agents, pigments, colouring matters, proces ⁇ sing aids and other types of additives, all of which are com ⁇ mon and well known to a person skilled in the art.
  • additives such as heat and UV stabili ⁇ zers, antistatic agents, pigments, colouring matters, proces ⁇ sing aids and other types of additives, all of which are com ⁇ mon and well known to a person skilled in the art.
  • the polymer composition of the invention will have a melt index in the range of from 0.5 to 400 g/10 min determined o according to ASTM D 1238 at 230 °C and 2.16 kg load.
  • the phe ⁇ nolic polymer has a considerably lower viscosity than the polyolefin resin, and as a result the melt index of the final composition will depend on the crosslinking degree of the phe ⁇ nolic polymer. Consequently, a low degree of crosslinking will 5 result in a high melt index, and vice versa. Therefore, the polymer composition has a melt index preferably in the range of 0.5-100 g/10 min, more preferred in the range of 0.5-50 g/10 min, and still more preferred in the range of 0.5-10 g/10 min.
  • the polymer composition of the invention is prepared by firstly heating the polyolefin resin and the thermoplastic phenolic polymer to a temperature above the melting tempera ⁇ ture of the highest-melting component. To ensure a satisfa- ctory melting of the components they should be heated to at least 160 ⁇ C, however the temperature should not exceed appro ⁇ ximately 275 C C in order to avoid an unwanted degradation of the polymers. A temperature range of from 180 to 240 °C is preferred. In the presence of oxygen, e.g. when exposed to air, polymers in a melted state will rapidly oxidize and de ⁇ grade. All processing at elevated temperatures should there ⁇ fore be performed in an inert atmosphere, e.g.
  • the polymer composition of the invention will become a true polymer alloy. It is appropriate to perform all these operations simultaneously in a mixer, for example in a batch mixer, or more preferred in an extruder.
  • the polyolefin resin, the phenolic polymer, the crosslinking agent and the catalyst may be fed to the mixer or extruder in any appropriate way.
  • the polymeric components could be pre ixed with common addi ⁇ tives, such as stabilizers, processing aids and other conven ⁇ tional additives well known to any person skilled in the art. For example, all components could be premixed and then fed together to the mixer.
  • an extruder the simplest procedure nor ⁇ mally will be to feed the components separately and then com ⁇ bine them in the hopper.
  • the polymer components should be in a melted state when the catalyst is added. In an extruder this may appropriately be achieved by feeding the catalyst through a separate inlet port in the barrel at a position downstream the hopper.
  • the polymer composition is prepared with a polypro ⁇ pylene resin as the matrix, with which resin the phenolforma ⁇ ldehyde is blended.
  • the phenolformaldehyde is then crosslinked 5 to form an interpenetrating network.
  • phenolformaldehyde of medium vis ⁇ cosity in an amount from 2.5 % to 10 % by weight is blended with the polypropylene matrix and is then crosslinked by the use of either hexamethylenetetramine, polyoxymethylene or o paraformaldehyde.
  • the amount of added crosslinking agent varies from 1 % to 3 % by weight of the quantity of phenolic polymer.
  • FIGS. 1 and 2 are photographs taken at 2000X magnification.
  • Figure 1 shows a composition of the 0 invention ottained by using paraformaldehyde as the crosslin ⁇ king agent (Example 8), while Figure 2 shows a composition obtained without using any crosslinking agent (Comparative Example 7) .
  • Figure 1 reveals that a network was created in the polypropylene phase, i.e. that a semi-IPN structure had been 5 formed.
  • compositions of the invention have significantly improved moduli of elasticity in relation to the comparative resins "P401" and "P410", and several of them also show improved impact resistances and in ⁇ creased elongations at break.
  • Figure 6 shows how the modulus of elasticity (repre ⁇ sented by the askew parallel lines in the figure) varies for a composition of the invention containing 2.5 % by weight of phenolformaldehyde crosslinked with 1 % to 3 % by weight of s hexamethylenetetramine and containing up to 5 % by weight of EPDM-g-MAH.
  • Figure 7 is similar to Figure 6, except that the com ⁇ position contains 10 % by weight of phenolformaldehyde.
  • Figures 6 and 7 show that the composition containing 0 2.5 % by weight of phenolformaldehyde will achieve the highest modulus of elasticity with a small content of EPDM-g-MAH, while the modulus of elasticity of the composition containing 10 % by weight of phenolformaldehyde is dependent only to a small extent of the EPDM-g-MAH content.
  • Figures 10 and 11 are similar to Figures 6 and 7, except that paraformaldehyde is used as the crosslinking agent. The modulus of elasticity of the compositions increases with increasing EPDM-g-MAH contents.
  • Figures 6 to 11 show that the modulus of elasticity o increases with increasing contents of phenolformaldehyde and crosslinking agent for all the compositions, even though the effect of the crosslinking agent are not equally strong for all of them.
  • a virgin poly ⁇ propylene resin, a homopolymer or copolymer has a modulus of elasticity within the range of from 600 to 1500 MPa.
  • compositions of the invention are very versatile resins which may be used alone or in admixtures with other resins intended for many end uses and for the industrial manu- facturing of various articles. For instance they may be inclu ⁇ ded into polypropylene compounds to provide them with improved mechanical properties, such as an improved modulus of elasti ⁇ city and impact resistance, and also to increase the adhesion properties. Further, the present compositions can provide polypropylene resins with flame retardant properties. Both for this reason and because of their good mechanical properties the present compositions are suitable for use in furnishing articles, e.g. in articles used in automobile compartments and in other automobile parts; electric cable isolations having an increased oxygen index; and in packaging materials for parti ⁇ cular end uses.
  • Examples 1 to 11 are to elucidate how different types of phenolformaldehydes, crosslinking agents and catalysts influence the properties of the final composi ⁇ tions.
  • Examples 12 to 24 the effects that various amounts of phenolformaldehyde, crosslinking agents and EPDM-g-MAH have on the modulus of elasticity (E modulus) of the final mate- rial, the elongation at break and the impact resistance at 0 ⁇ C are investigated.
  • E modulus modulus of elasticity
  • the phenol polymer used in Examples 1 to 4 was a phe ⁇ nolformaldehyde of high viscosity. In the remaining examples phenolformaldehyde of medium viscosity was used. Types and quantities of the components used in the preparations of the polymer compositions, as well as the pro ⁇ perties of the final materials, are given in Table 1 for Exam ⁇ ples 1 to 11 and in Table 2 for Examples 12 to 31.
  • compositions of all the examples were processed in a 25 mm "Clextral" twin screw extruder having a ratio L/D « 34 and co-rotating screws.
  • the extruder temperatures were kept within the range of from 180 to 225 ⁇ C.
  • the screw rotation speed was 150 rpm and the throughput 3 kg/h.
  • the materials were extruded as strands which were quenched in water, dried and then granulated by methods well known per se.
  • Test specimens were manufactured from the obtained granulated material and were used for determining the proper ⁇ ties of the compositions.
  • the modulus of elasticity values were obtained in accordance with ISO 527 from the stress-strain curve recorded at the tensile testing of the specimens.
  • the impact resistance values were obtained in accor ⁇ dance with an ISO method by using an apparatus comprising a falling dart equipped with a sensor registering the impact energy at the moment of strike.
  • the weighted dart is dropped onto a disk of the material to be tested and the impact energy is calculated from the sensor signal.
  • Each disk had a speci ⁇ fied thickness, e.g. 1 mm or 3 mm, and temperature, typically 0 ⁇ C.
  • the dynamic viscosities of the composition resins were determined by using a parallel plate viscosimeter at the frequencies of 0.05 Hz and 100 Hz, designated as ⁇ 005 and ⁇ 100 , respectively in Table 3.
  • Example 1 The method of Example 1 was used, except that no catalyst or crosslinking agent were used. The results are re ⁇ ported in Table 1.
  • Example 1 The method of Example 1 was used, except that 15 % by weight of phenolformaldehyde as well as 1 % by weight of para ⁇ formaldehyde added as a crosslinking agent were fed to the extruder. No catalyst was added. The results are reported in Table 1.
  • Example 3 The method of Example 3 was used, except that 0.5 % by weight of Mg(0H) 2 was used as a catalyst and no crosslinking agent was added. The results are reported in Table 1. Examples 5 and 6
  • Example 7 (Comparative example) The method of Example 5 was used, except that 10 % by weight of phenolformaldehyde and no crosslinking agent and no catalyst were used. The results are reported in Table 2.
  • Example 8 The method of Examples 5 and 6 was used, except that
  • Example 8 The method of Example 8 was used, except that 5 % by weight of paraformaldehyde as a crosslinking agent and 1 % by weight of magnesium hydroxide as a catalyst were used. The results are reported in Table 2.
  • Example 8 The method of Example 8 was used, except that 5 % by weight of polyoxymethylene as a crosslinking agent was used. The results are reported in Table 2.
  • Example 9 The method of Example 9 was used, except that 30 % by weight of formaldehyde was used, while the catalyst was omit ⁇ ted. The results are reported in Table 2.
  • Examples 1 and 3 and Comparative Example 2 show that paraformaldehyde is a crosslinking agent of low effi ⁇ ciency since no or only a weak increase in the modulus of elasticity is obtained, while the elongation at break and i - pact resistance do not change significantly.
  • Examples 5 and 10 demonstrate that 5 % by weight of polyoxymethylene added as a crosslinking agent results in a substantial increase in the modulus of elasticity in relation s to the composition of Comparative Example 7 where no crosslin ⁇ king agent was used.
  • Example 6 demonstrates that an increase of the amount of polyoxymethylene to 10 % by weight gives a further increase in the modulus of elasticity, while the elon ⁇ gation at break and impact resistance are reduced.
  • Example 8 demonstrates that hexamethylenetetramine as a crosslinking agent results in a substantially higher modulus of elasticity compared with Comparative Example 7, while the elongation at break and impact resistance show no substantial change.
  • Examples 9 and 11 demonstrate, compared with Com ⁇ parative Example 7, that paraformaldehyde is a low efficient crosslinking agent. This supports the results from Examples 1 and 3 discussed above.
  • Example 12 The method of Examples 12 to 14 was followed, except that the paraformaldehyde crosslinking agent was used in an amount of 3 % by weight. In Examples 16 and 17 also 5 % by weight of EPDM-g-MAH was added. Experimental details and ob- 5 tained results are presented in Table 3.
  • Examples 28 to 31 The polypropylene and 2.5 %, 2.5 %, 5 % and 10 % by weight, respectively, of phenolformaldehyde polymer and 3 % by weight of polyoxymethylene as a crosslinking agent were used. In Examples 29 and 30 also 5 % by weight of EPDM-g-MAH was added. Otherwise, the procedure was as in Examples 25 to 27. Experimental details and obtained results are presented in Table 3. Table 1
  • Phenolformaldehyde polymer (PF) of low viscosity (“high flow”). Impact resistance determined on dishes of thickness 3 mm.
  • Crosslinking agent Paraformaldehyde having 5 to 15 repeating units.

Abstract

Cette invention se rapporte à une composition polymère ayant un réseau interpénétrant, qui comprend une matrice de polyoléfine et, éventuellement, une petite quantité d'un polymère éthylène/propylène/butadiène greffé avec de l'anydride maléique, ainsi que, uniformément réparti dans cette matrice, un polymère phénolique thermoplastique, lequel a été réticulé avec un agent de réticulation jusqu'à un degré de réticulation compris entre 0,5 et 50 %, formant ainsi un réseau interpénétrant dans ladite matrice, cette matrice constituant 99 % à 5 % en poids de la composition et la résine phénolique partiellement réticulée constituant 1 à 95 % en poids de la composition. Un procédé pour produire cette composition polymère consiste à mélanger la résine de la matrice et le polymère phénolique par malaxage en continu, de préférence dans une atmosphère inerte, tout en la chauffant à une température supérieure à la température de fusion du constituant ayant le plus haut point de fusion, jusqu'à ce que le polymère phénolique soit réticulé à un degré de réticulation désiré, le produit ainsi obtenu étant alors refroidi et granulé.
PCT/NO1995/000171 1994-09-23 1995-09-22 Composition polymere contenant un reseau interpenetrant WO1996009346A1 (fr)

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AU36207/95A AU3620795A (en) 1994-09-23 1995-09-22 Polymer composition containing interpenetrating network

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NO943544 1994-09-23
NO943544A NO943544L (no) 1994-09-23 1994-09-23 Polymermateriale med interpenetrerende nettverk og fremgangsmåte for fremstilling av dette

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0104106A2 (fr) * 1982-08-26 1984-03-28 The Bendix Corporation Mélanges de polymères thermoplastiques ayant plusieurs composants
EP0202430A1 (fr) * 1985-03-26 1986-11-26 Mitsubishi Petrochemical Co., Ltd. Compositions de polyoléfine et une charge minérale
EP0426482A2 (fr) * 1989-11-01 1991-05-08 Polyplastics Co. Ltd. Compositions de résines thermoplastiques contenant des charges et ayant une phase interpénétrante avec une structure de réseau tridimensionnelle et son procédé de fabrication par mélange à l'état fondu

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0104106A2 (fr) * 1982-08-26 1984-03-28 The Bendix Corporation Mélanges de polymères thermoplastiques ayant plusieurs composants
EP0202430A1 (fr) * 1985-03-26 1986-11-26 Mitsubishi Petrochemical Co., Ltd. Compositions de polyoléfine et une charge minérale
EP0426482A2 (fr) * 1989-11-01 1991-05-08 Polyplastics Co. Ltd. Compositions de résines thermoplastiques contenant des charges et ayant une phase interpénétrante avec une structure de réseau tridimensionnelle et son procédé de fabrication par mélange à l'état fondu

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DIALOG INFORMATION SERVICES, File 347, JP0 & JAPIO, Dialog Accession No. 04052054, KAWASAKI STEEL CORP, "Polypropylene-Based Resin Composition"; & SECTION: C, Section No. 1077, Vol. 17, No. 345, Pg. 83, June 30, 1993, (19930630). *

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