CN1094957C

CN1094957C - Process for preparing composite board of fluorine-resistant fluoroethane for refrigerator

Info

Publication number: CN1094957C
Application number: CN00104584A
Authority: CN
Inventors: 刘景江; 陈广新; 周华荣; 孙春荣
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2000-03-25
Filing date: 2000-03-25
Publication date: 2002-11-27
Anticipated expiration: 2020-03-25
Also published as: CN1306037A

Abstract

The present invention relates to an HCFC substance resisting composite board material for an inner lining of an electric refrigerator. A blocking layer of the composite board material is prepared from HIPS, SBS, nylon 1010, maleic anhydride grafted HIPS resin, a small quantity of antioxidant ky-7910, an antiaging agent 264, etc. In the process of the extrusion moulding of the composite board material, blocking resin moves along an upper die lip, a base board moves along a lower die lip, and the temperature of the die lips and the temperature of a head zone of a screw machine are controlled as 220DEG C. The obtained composite board material has outstanding mechanical performance and outstanding HCFC-141b blocking performance.

Description

The preparation method of the refrigerator of anti-chlorine, fluoroethane material (cabinet) composite sheet

The invention belongs to the preparation method of anti-chlorine, fluoroethane (HCFC) material refrigerator (cabinet) composite sheet.

Be that refrigerator (cabinet) liner of matrix is made by two big class materials with high-impact polystyrene (HIPS) in the prior art.One class is the common sheet material of HIPS.This class sheet material is in the refrigeration equipment of whipping agent and refrigeration agent applicable to fluorine Lyons and hydrocarbon polymer (as pentamethylene).The ozonosphere in the atmospheric layer was destroyed in fluorine Lyons, did not all allow to carry out the production of this class material from countries in the world in 2000 again.Hydrocarbon polymer is inflammable, explosive.During use, manufacturer will increase a large amount of fire prevention, antiknock device investment and will be strictly on guard against in user's use owing to leak the blast that causes.The composite sheet that the second class liner then is made of above-mentioned common sheet material and barrier layer.Be generally used for adopting HCFC-141b (CH ₃CCl ₂F) be whipping agent, with HFC-134a (CH ₂FCF ₃) be in the refrigeration equipment of refrigeration agent.This whipping agent and refrigeration agent do not destroy ozone in the atmospheric layer and nonflammable basically.But its solvation is very capable, can make the deliquescing of common HIPS liner, bubble, erodes away the cavity.The ruined phenomenon of liner then can not appear at the composite sheet that is added with barrier layer with the contacted one side of whipping agent.Because barrier layer can intercept seeing through of HCFC material effectively.

In the prior art, U.S.US5, the three-layer composite board that used material is made up of top layer and internal layer in 264,280 patents.Its mesexine is polystyrene and partially hydrogenated styrene-butadiene copolymer.Internal layer is by polyolefine, and vinylbenzene-undersaturated anhydride multipolymer is formed.The poor-performing of its top layer material of anti-HCFC.Self does not absorb the HCFC material internal layer polyolefine, and still, they are relatively poor to the barrier property of HCFC.The barrier property of nylon is best in a few class barrier materials such as polyolefine, polyester, nylon, and polyester takes second place.The fusing point of nylon 66 and nylon 6 is very high in nylon family, is respectively 255 ℃ and 232 ℃, and degraded and crosslinked usually takes place under this higher processing temperature HIPS, and resulting sheet material turns to be yellow and gel piece is arranged, so that can't become inner container of icebox by plastic uptake.Ni Long11 and 12 processing temperatures with HIPS are complementary.But price is very expensive.The fusing point of nylon 1010 is 192 ℃, and close and excellent barrier property is arranged with the HIPS processing temperature, price only is about 1/3rd of a Ni Long11.Existing many reports about nylon 1010 and HIPS blending study in the document are as " functional polymer journal, 1998,11 (4), 506, " the HIPS/MA graft copolymer are to the increase-volume of HIPS/PA co-mixing system " in research paper such as Chen Guangxin, Liu Jingjiang; The polymer journal, 1999,5,557, " nylon 1010 respectively with the co-mixing system research of the HIPS of grafting and grafted maleic anhydride not "; J.Appl.Poly m.Sci., 1999,71 (12), 2017, " Preparation of HIPS/MA graft copolymer and itscompatibilization in HIPS/PA1010 blens " " HIPS/ nylon 1010 co-mixing system there is detailed research.Yet these reports all are that research is external phase with the nylon 1010, and HIPS is the basic science problem of the phase of loosing.Because nylon 1010 is relatively poor with the adhesive property of HIPS interlaminar resin, extrudes composite sheet with this blend with HIPS splitting can take place, and can't become inner container of icebox by plastic uptake.Owing to do not add toughner, this composition board material is crisp also to be to restrict it to be able to the one of the main reasons of practical application in refrigerating industry.

The preparation method who the purpose of this invention is to provide a kind of refrigerator (cabinet) composite sheet of the material of anti-HCFC.Selecting the HIPS resin is main component, nylon 1010 is disperse phase and is added with expanding material, toughner, anti-aging agent, oxidation inhibitor and obtains blend in order to the preparation barrier layer, with the HIPS sheet material resins substrate of common refrigerator, by extruding the composite sheet that the compound way makes the material of anti-HCFC.Thereby realized the overall equilbrium of the multiple excellent properties such as barrier, toughness and processing plastics sucking moulding of good interface bonding, excellence between barrier layer and the substrate.

Because the barrier layer resin is to be base material with HIPS, thereby guaranteed that it is with excellent interface bonding is arranged between the HIPS substrate.With the end amido reaction of nylon 1010, original position generates HIPS and nylon 1010 multipolymer in extruding the blend process for maleic anhydride and HIPS graft copolymer.It is the excellent expanding material of HIPS with nylon 1010, has significantly improved two alternate interface performances.SBS has increased the material toughness.The resin of extruding prolongs through three roll-ins and becomes composite sheet.Have only the control barrier layer to go on die lip and could guarantee that the barrier layer in the composite sheet bears shearing action in the three roll-in processes of prolonging, smooth surface and nylon 1010 are lamellar morphologies, thereby make composite sheet have excellent barriering effect.

The prepared barrier resins of the present invention is made up of following material in weight percent: 100 parts of HIPS resins, nylon 1010 resin 20-30 part, HIPS resin 1-8 part of maleic anhydride graft, wherein the percentage of grafting of maleic anhydride in the HIPS resin is 1-5wt%, the styrene-butadiene-styrene triblock copolymer, the SBS thermoplastic elastomer wherein weight ratio of S/B is 30/70,2-5 part, 0.5 part of four (β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid) 0.5 part of tetramethylolmethane (oxidation inhibitor ky-7910) and 2,6 ditertbutylparacresol (antioxidant 264); Extrusion moulding is to be finished by two single screw extrusion machines, wherein the common substrate of HIPS is extruded by the screw rod of φ 90mm, the barrier layer resin is extruded by the screw rod of φ 60mm, material ratio is 90: 10, the two kinds of resins in die lip place converge, wherein the substrate material is walked lower floor, intercepts layered material and goes on layer, and temperature all is controlled at 220 ℃.

The socle girder notched Izod impact strength that is made composite sheet by prescription provided by the invention and forming technique can reach 80-110J/m, modulus in flexure is 1400-1700MPa, elongation at break is 30-40%, tensile strength is 18-22MPa, heat-drawn wire is 75-80 ℃, barrier layer sheet material is placed under room temperature HCFC-141b saturated vapor pressure and was absorbed the HCFC-141b value in 24 hours less than 5% of deadweight, only is 1/5th of polyolefine isolation-type sheet material absorbed dose.

Embodiment provided by the invention is as follows:

Embodiment 1:

Consisting of of a kind of corrosive of anti-HCFC-141b inner container of electric refrigerator its barrier layer resin of composite sheet: 100 parts of HIPS resins, 20 parts of nylon 1010 resins, percentage of grafting is 3 parts of the maleic anhydride graft HIPS resins of 3wt%, SBS3 part stirs in homogenizer with oxidation inhibitor ky-7910 and 0.5 part of antioxidant 264 of 0.5 part, with twin screw extruder extrude, granulation.

The resin that barrier layer resin that will make with aforesaid method and HIPS common refrigerator sheet material are used is respectively charged in the hopper of φ 60mm and φ 90mm single screw extrusion machine, adopts the forming method extrusion moulding of common composite sheet.But the control barrier resins is gone on die lip, and common plate timber fat is gone down die lip, and the temperature of forcing machine Head Section and die lip is controlled at 220 ℃.The socle girder notched Izod impact strength of resulting composite sheet can reach 90J/m, modulus in flexure is 1600MPa, elongation at break is 35%, tensile strength is 20MPa, heat-drawn wire is 78 ℃, and barrier layer sheet material is placed 24 hours absorption HCFC-141b values and is 4.6% of deadweight under room temperature HCFC-141b saturated vapor pressure.

Embodiment 2:

Consisting of of a kind of corrosive of anti-HCFC-141b refrigerator lining its barrier layer resin of composite sheet: 100 parts of HIPS resins, 30 parts of nylon 1010 resins, percentage of grafting is 5 parts of the maleic anhydride graft HIPS resins of 5wt%, 5 parts of SBS stir in homogenizer with oxidation inhibitor ky-7910 and 0.5 part of antioxidant 264 of 0.5 part, with twin screw extruder extrude, granulation.

The resin that barrier layer resin that will make with aforesaid method and HIPS common refrigerator sheet material are used is respectively charged in the hopper of φ 60mm and φ 90mm single screw extrusion machine, adopts the forming method extrusion moulding of common composite sheet.But the control barrier resins is gone on die lip, and common plate timber fat is gone down die lip, and the temperature of forcing machine Head Section and die lip is controlled at 220 ℃.The socle girder notched Izod impact strength of resulting composite sheet can reach 100J/m, modulus in flexure is 1500MPa, elongation at break is 35%, tensile strength is 19MPa, heat-drawn wire is 80 ℃, and barrier layer sheet material is placed 24 hours absorption HCFC-141b values and is 3.9% of deadweight under room temperature HCFC-141b saturated vapor pressure.

Claims

1, a kind of anti-chlorine, the preparation method of fluoroethane material refrigerator (cabinet) composite sheet, it is characterized in that prepared barrier resins is made up of following material in parts by weight: 100 parts of high-impact polystyrene resins, nylon 1010 resin 20-30 part, high-impact polystyrene resin 1-8 part of maleic anhydride graft, wherein the percentage of grafting of maleic anhydride in high-impact polystyrene resin is 1-5wt%, vinylbenzene and divinyl weight ratio are styrene-butadiene-styrene triblock copolymer 2-5 part of 30/70,0.5 part of four (β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid) 0.5 part of tetramethylolmethane and 2,6 ditertbutylparacresol; Extrusion moulding is to be finished by two single screw extrusion machines, wherein the common substrate of high-impact polystyrene is extruded by the screw rod of φ 90mm, the barrier layer resin is extruded by the screw rod of φ 60mm, material ratio is 90: 10, the two kinds of resins in die lip place converge, wherein the substrate material is walked lower floor, intercepts layered material and goes on layer, and temperature is controlled at 220 ℃.

2, the preparation method of anti-chlorine as claimed in claim 1, fluoroethane material refrigerator (cabinet) composite sheet, the high-impact polystyrene resin that it is characterized in that used maleic anhydride graft is 3-5 part.

3, the preparation method of anti-chlorine as claimed in claim 1, fluoroethane material refrigerator (cabinet) composite sheet is characterized in that the percentage of grafting in the high-impact polystyrene resin of used maleic anhydride graft is 3-5wt%.