CN100448902C - Acrylic resin with high bath strength, and preparation method - Google Patents
Acrylic resin with high bath strength, and preparation method Download PDFInfo
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- CN100448902C CN100448902C CNB2006100171814A CN200610017181A CN100448902C CN 100448902 C CN100448902 C CN 100448902C CN B2006100171814 A CNB2006100171814 A CN B2006100171814A CN 200610017181 A CN200610017181 A CN 200610017181A CN 100448902 C CN100448902 C CN 100448902C
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Abstract
This invention relates to a method for preparing polypropylene resin with high melt strength. The polypropylene resin is composed of: component A 70-99.8 wt.%, component B 0.1-29.9 wt.% (preferential 0.1-20 wt.%), and component C 0..1-25 wt.% (preferential 0.1-10 wt.%). Component A is natural polypropylene resin. Component B is vinyl polybutadiene. Component C is acrylate compound. The method comprises: uniformly mixing the above components, loading into a melt-grafting reactor, and melt-grafting at 190-240 deg.C to obtain polypropylene resin with high melt strength. The obtained polypropylene resin has high melt strength without sacrifice of mechanical properties.
Description
Technical field
The present invention relates to a kind of high bath strength acrylic resin and preparation method thereof
Background technology
Polypropylene is a kind of widely used general-purpose plastics, and it possesses the performance of many excellences, as little, the tasteless odorless of relative density, anti-edible oil, excellent corrosion resistance, electrical property with chemical stability is good and price is low, output is big, is only second to PVC and PE.But the polypropylene poor toughness, fragile under low temperature disconnected, heat-drawn wire is not high; And polyacrylic chain structure is linear, and under the molten state, polypropylene does not have strain hardening effect, causes the low and refractory of its melt strength shortcomings such as poor performance of hanging down, and therefore limited polyacrylic application greatly.Simultaneously, polyacrylic softening temperature and fusing point are approaching, after temperature is higher than fusing point, the viscosity of its melt strength and melt sharply descends, product wall thickness inequality when causing thermoforming is extruded, is coated with, is occurred when rolling edge curl and shrinks, abscess problem such as subside during extrusion foaming.Therefore, have the polypropylene of strain hardening effect under the exploitation molten state, promptly high melt strength, propylene is imperative.
At present, preparation high melt strength, propylene method mainly is divided into two big classes: a class is that polypropylene and other compounds carry out reaction modifying; Another kind of is that polypropylene and other polymkeric substance carry out blending and modifying.Specific implementation method mainly contains: x ray irradiation x method, reaction extrusion molding, post polymerization still method, solution grafting, dynamic crosslinking method, melt blending modification method etc.
Patent CN1045107A, CN1055372A have set forth and have adopted superoxide initiation grafting modified polypropene powder in polymeric kettle to obtain having the acrylic resin of strain hardening.Another patent (CN1432596A) adopts 2,5 dimethyl-2,5 pair 8 tert-butyl hydroperoxide hexanes and diacrylate-1, the acetone soln mixing of 6-butanediol ester joins twin screw by injection and extrudes in the melt of polypropylene powder, carry out grafting, obtain high bath strength acrylic resin.One piece of open report (Journal of Applied Polymer Science, vol.61,1395～1404,1996) adopts polypropylene and polyfunctional monomer pentaerythritol triacrylate to react in the presence of superoxide can make high melt strength, propylene.Another piece of writing report (Journal ofApplied Polymer Science, vol.66,809～819,1997) adopt polypropylene and polyethylene, trimethylammonium triacrylate under the effect of superoxide, extrude the high melt strength, propylene of preparation branching by twin screw.In addition, adopt acrylic ester monomer in addition under peroxidation, carry out fusion-grafting with polypropylene and can prepare high branched p 0 lypropylene resin (" Chinese plastics ", the 16th volume, the 10th phase, 24～28,2002).From above-mentioned report, as can be seen, in preparation high melt strength, propylene process, all adopt superoxide as initiator.Yet the introducing of superoxide can make polypropylene that degraded significantly takes place, and reduces polyacrylic mechanical property greatly.In addition, also can increase the cost of high bath strength acrylic resin product, reduce the competitive position of product in market.
Summary of the invention
The object of the present invention is to provide a kind of high bath strength acrylic resin.
Another object of the present invention provides a kind of preparation method of high bath strength acrylic resin.
Technology implementation scheme of the present invention is as follows:
High bath strength acrylic resin, it is made up of A component, B component and C component: wherein the weight percent of A component is 70%～99.8%, and the weight percent of B component is 0.1%～29.9%, and the weight percent of C component is 0.1%～25%;
The optimized scope of the weight percent of described B component is 0.1%～20%, and the optimized scope of the weight percent of C component is 0.1%～10%.
Wherein the A component is ecosystem acrylic resin (is called for short PP), and so-called " ecosystem acrylic resin " is the acrylic resin that does not add any auxiliary agent, come out by direct production in the polymeric kettle.
The B component is 50%～98% vinyl polybutadiene for the contents of ethylene molar ratio; Preferential selection contents of ethylene molar ratio is 70%～98% vinyl polybutadiene.
The C component is an esters of acrylic acid: Viscoat 295 (TMPTA), ethoxylated trimethylolpropane triacrylate (EO
3-TMPTA), propoxylation Viscoat 295 (PO
3-TMPTA), trimethylolpropane trimethacrylate (TMPTMA), glycerol propoxylate triacrylate (PO
3-GTA), pentaerythritol triacrylate (PETA), 1,4 butanediol diacrylate (BDDA) or 1,6 hexanediol diacrylate (HDDA).
Preparation method of the present invention is:
(1), melting graft reaction equipment is chosen twin screw extruder or single screw extrusion machine; With the A component, B component and C component mix by proportioning, join the material chamber from the spout of twin screw extruder or single screw extrusion machine, carry out melting graft reaction, twin screw extruder or single screw extrusion machine revolution are 20～300 rev/mins, it is four heating zone that twin screw extruder or single screw extrusion machine are divided into, wherein, one Heating Zone Temperature is set at 190 ℃～230 ℃, two Heating Zone Temperature are set at 200 ℃～240 ℃, three Heating Zone Temperature are set at 200 ℃～240 ℃, four Heating Zone Temperature are set at 200 ℃～240 ℃, and extruding pelletization obtains high bath strength acrylic resin.
(2), melting graft reaction equipment is chosen Banbury mixer; A component, B component and C component are mixed by proportioning, join the material chamber, carry out melting graft reaction from the spout of Banbury mixer, temperature of reaction is set at 190 ℃～240 ℃, reaction times is 1～15 minute, finishes reaction, obtains high bath strength acrylic resin.
The testing tool that the present invention adopts in an embodiment is as follows:
The tensile property test: adopt the Inxtron material experiment-machine, draw speed is 50mm/min;
Tc is measured: adopt DSC;
Melt index determination: adopt SRZ-400D type melt flow rate (MFR) determinator;
Melt strength is measured: adopt RHEOTENS 71.97 melt strength determinators.
Abandoning tradition of the present invention uses the method for superoxide initiation grafting reaction to prepare high bath strength acrylic resin, adopts original position thermal initiation grafted method to prepare high bath strength acrylic resin.This method is simple, convenient, need not to introduce peroxide initiator, can directly apply to the plain polypropylene resin modified of present production, produce high bath strength acrylic resin, thereby saved human and material resources and financial resources, improved the status of high bath strength acrylic resin in market competition.
Specific embodiment is as follows.
Embodiment 1
Be 99.8% to take by weighing polypropylene 2994 gram by weight percentage, weight percent is that 0.1% to take by weighing the contents of ethylene molar ratio be 96% vinyl polybutadiene, 3 grams, weight percent is 0.1% to take by weighing Viscoat 295 3 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 20 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 190 ℃, two Heating Zone Temperature are set at 210 ℃, and three Heating Zone Temperature are set at 240 ℃, and four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 2
Be 98% to take by weighing polypropylene 2940 gram by weight percentage, weight percent is that 1% to take by weighing the contents of ethylene molar ratio be 96% vinyl polybutadiene, 30 grams, weight percent is 1% to take by weighing Viscoat 295 30 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 70 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 200 ℃, and three Heating Zone Temperature are set at 200 ℃, and four Heating Zone Temperature are set at 200 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 3
Be 97% to take by weighing polypropylene 2910 gram by weight percentage, weight percent is that 2% to take by weighing the contents of ethylene molar ratio be 96% vinyl polybutadiene, 60 grams, weight percent is 1% to take by weighing Viscoat 295 30 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 100 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 240 ℃, and three Heating Zone Temperature are set at 240 ℃, and four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 4
Be 98% to take by weighing polypropylene 2940 gram by weight percentage, weight percent is that 0.5% to take by weighing the contents of ethylene molar ratio be 96% vinyl polybutadiene, 15 grams, weight percent is 1.5% to take by weighing Viscoat 295 45 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 150 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 240 ℃, three Heating Zone Temperature are set at 230 ℃, four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 5
Be 97% to take by weighing polypropylene 2910 gram by weight percentage, weight percent is that 1% to take by weighing the contents of ethylene molar ratio be 93% vinyl polybutadiene, 30 grams, weight percent is 2% to take by weighing Viscoat 295 60 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 220 ℃, two Heating Zone Temperature are set at 220 ℃, and three Heating Zone Temperature are set at 220 ℃, and four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 6
Be 95% to take by weighing polypropylene 2850 gram by weight percentage, weight percent is that 4.9% to take by weighing the contents of ethylene molar ratio be 93% vinyl polybutadiene, 147 grams, weight percent is 0.1% to take by weighing trimethylolpropane trimethacrylate 3 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 250 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 190 ℃, two Heating Zone Temperature are set at 240 ℃, three Heating Zone Temperature are set at 240 ℃, four Heating Zone Temperature are set at 240 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 7
Be 96% to take by weighing polypropylene 2880 gram by weight percentage, weight percent is that 2% to take by weighing the contents of ethylene molar ratio be 96% vinyl polybutadiene, 60 grams, weight percent is 2% to take by weighing Viscoat 295 60 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 300 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 190 ℃, two Heating Zone Temperature are set at 220 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 240 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 8
Be 95% to take by weighing polypropylene 2850 gram by weight percentage, weight percent is that 2% to take by weighing the contents of ethylene molar ratio be 93% vinyl polybutadiene, 60 grams, weight percent is 3% to take by weighing Viscoat 295 90 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 210 ℃, two Heating Zone Temperature are set at 230 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 9
Be 94.99% to take by weighing polypropylene 2850 gram by weight percentage, weight percent is that 3% to take by weighing the contents of ethylene molar ratio be 93% vinyl polybutadiene, 90 grams, weight percent is 2% to take by weighing Viscoat 295 60 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 230 ℃, two Heating Zone Temperature are set at 230 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 10
Be 90% to take by weighing polypropylene 2700 gram by weight percentage, weight percent is that 3% to take by weighing the contents of ethylene molar ratio be 91% vinyl polybutadiene, 90 grams, weight percent is 7% to take by weighing Viscoat 295 210 gram, in stirrer behind the uniform mixing 20min, join and carry out melting graft reaction in the Banbury mixer, temperature is set at 210 ℃, and frit reaction is after 1 minute, finish reaction, obtain high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 11
Be 90% to take by weighing polypropylene 2700 gram by weight percentage, weight percent is that 7% to take by weighing the contents of ethylene molar ratio be 98% vinyl polybutadiene, 210 grams, weight percent is 3% to take by weighing Viscoat 295 90 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 210 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 240 ℃, two Heating Zone Temperature are set at 240 ℃, and three Heating Zone Temperature are set at 240 ℃, and four Heating Zone Temperature are set at 240 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 12
Be 85% to take by weighing polipropene 25 50 gram by weight percentage, weight percent is that 5% to take by weighing the contents of ethylene molar ratio be 91% vinyl polybutadiene, 150 grams, weight percent is 10% to take by weighing Viscoat 295 300 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 230 ℃, and three Heating Zone Temperature are set at 240 ℃, and four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 13
Be 85% to take by weighing polipropene 25 50 gram by weight percentage, weight percent is that 10% to take by weighing the contents of ethylene molar ratio be 91% vinyl polybutadiene, 300 grams, weight percent is 5% to take by weighing Viscoat 295 150 gram, in stirrer behind the uniform mixing 20min, join and carry out melting graft reaction in the Banbury mixer, temperature is set at 190 ℃, and frit reaction is after 15 minutes, finish reaction, obtain high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 14
Be 80% to take by weighing polypropylene 2400 gram by weight percentage, weight percent is that 10% to take by weighing the contents of ethylene molar ratio be 98% vinyl polybutadiene, 300 grams, weight percent is 10% to take by weighing Viscoat 295 300 gram, in stirrer behind the uniform mixing 20min, join and carry out melting graft reaction in the Banbury mixer, temperature is set at 240 ℃, and frit reaction is after 10 minutes, finish reaction, obtain high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 15
Be 75% to take by weighing polypropylene 2250 gram by weight percentage, weight percent is that 10% to take by weighing the contents of ethylene molar ratio be 91% vinyl polybutadiene, 300 grams, weight percent is 15% to take by weighing Viscoat 295 450 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 240 ℃, three Heating Zone Temperature are set at 240 ℃, four Heating Zone Temperature are set at 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 16
Be 70% to take by weighing polypropylene 2100 gram by weight percentage, weight percent is that 5% to take by weighing the contents of ethylene molar ratio be 91% vinyl polybutadiene, 150 grams, weight percent is 25% to take by weighing Viscoat 295 750 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 230 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 17
Be 79.9% to take by weighing polypropylene 2397 gram by weight percentage, weight percent is that 20% to take by weighing the contents of ethylene molar ratio be 90% vinyl polybutadiene, 600 grams, weight percent is 0.1% to take by weighing glycerol propoxylate triacrylate 3 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 220 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 18
Be 84.9% to take by weighing polipropene 25 47 gram by weight percentage, weight percent is that 0.1% to take by weighing the contents of ethylene molar ratio be 90% vinyl polybutadiene, 3 grams, weight percent is 15% to take by weighing Viscoat 295 450 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 190 ℃, two Heating Zone Temperature are set at 240 ℃, three Heating Zone Temperature are set at 240 ℃, four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 19
Be 95% to take by weighing polypropylene 2850 gram by weight percentage, weight percent is that 2.5% to take by weighing the contents of ethylene molar ratio be 87% vinyl polybutadiene, 75 grams, weight percent is 2.5% to take by weighing Viscoat 295 75 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 230 ℃, three Heating Zone Temperature are set at 230 ℃, four Heating Zone Temperature are set at 220 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 20
Be 96% to take by weighing polypropylene 2880 gram by weight percentage, weight percent is that 1% to take by weighing the contents of ethylene molar ratio be 85% vinyl polybutadiene, 30 grams, weight percent is 3% to take by weighing Viscoat 295 90 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the single screw extrusion machine of 35mm, the revolution of forcing machine is set at 20 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 190 ℃, two Heating Zone Temperature are set at 220 ℃, and three Heating Zone Temperature are set at 240 ℃, and four Heating Zone Temperature are set at 200 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 21
Be 94% to take by weighing polypropylene 2820 gram by weight percentage, weight percent is that 3% to take by weighing the contents of ethylene molar ratio be 82% vinyl polybutadiene, 90 grams, weight percent is 3% to take by weighing Viscoat 295 90 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the single screw extrusion machine of 35mm, the revolution of forcing machine is set at 100 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 210 ℃, two Heating Zone Temperature are set at 240 ℃, and three Heating Zone Temperature are set at 240 ℃, and four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 22
Be 97% to take by weighing polypropylene 2910 gram by weight percentage, weight percent is that 1% to take by weighing the contents of ethylene molar ratio be 76% vinyl polybutadiene, 30 grams, weight percent is 2% to take by weighing Viscoat 295 60 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the single screw extrusion machine of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 230 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 240 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 23
Be 92% to take by weighing polypropylene 2760 gram by weight percentage, weight percent is that 2% to take by weighing the contents of ethylene molar ratio be 74% vinyl polybutadiene, 60 grams, weight percent is 6% to take by weighing 1,4-butylene glycol diacrylate 180 grams, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the single screw extrusion machine of 35mm, the revolution of forcing machine is set at 300 rev/mins, forcing machine is divided into four heating zone, and wherein a Heating Zone Temperature is set at 230 ℃, and two Heating Zone Temperature are set at 240 ℃, three Heating Zone Temperature are set at 240 ℃, four Heating Zone Temperature are set at 240 ℃, and extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 24
Be 89% to take by weighing polypropylene 2670 gram by weight percentage, weight percent is that 3% to take by weighing the contents of ethylene molar ratio be 70% vinyl polybutadiene, 90 grams, weight percent is 8% to take by weighing 1,6-hexanediyl ester 240 grams, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 220 rev/mins, forcing machine is divided into four heating zone, and wherein a Heating Zone Temperature is set at 200 ℃, and two Heating Zone Temperature are set at 220 ℃, three Heating Zone Temperature are set at 220 ℃, four Heating Zone Temperature are set at 210 ℃, and extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 25
Be 93% to take by weighing polypropylene 2790 gram by weight percentage, weight percent is that 3% to take by weighing the contents of ethylene molar ratio be 66% vinyl polybutadiene, 90 grams, weight percent is 4% to take by weighing pentaerythritol triacrylate 120 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 120 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 220 ℃, and three Heating Zone Temperature are set at 220 ℃, and four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1.
Embodiment 26
Be 94% to take by weighing polypropylene 2820 gram by weight percentage, weight percent is that 4% to take by weighing the contents of ethylene molar ratio be 65% vinyl polybutadiene, 120 grams, weight percent is 2% to take by weighing Viscoat 295 60 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 210 ℃, two Heating Zone Temperature are set at 230 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1
Embodiment 27
Be 88% to take by weighing polypropylene 2640 gram by weight percentage, weight percent is that 6% to take by weighing the contents of ethylene molar ratio be 63% vinyl polybutadiene, 180 grams, weight percent is 6% to take by weighing Viscoat 295 180 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 230 ℃, and three Heating Zone Temperature are set at 230 ℃, and four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1
Embodiment 28
Be 88% to take by weighing polypropylene 2640 gram by weight percentage, weight percent is that 2% to take by weighing the contents of ethylene molar ratio be 55% vinyl polybutadiene, 60 grams, weight percent is 10% to take by weighing propoxylation Viscoat 295 300 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 100 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 220 ℃, three Heating Zone Temperature are set at 220 ℃, four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1
Embodiment 29
Be 88% to take by weighing polypropylene 2640 gram by weight percentage, weight percent is that 8% to take by weighing the contents of ethylene molar ratio be 50% vinyl polybutadiene, 240 grams, weight percent is 4% to take by weighing ethoxylated trimethylolpropane triacrylate 120 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 220 ℃, three Heating Zone Temperature are set at 220 ℃, four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1
Embodiment 30
Be 85% to take by weighing polipropene 25 50 gram by weight percentage, weight percent is that 10% to take by weighing the contents of ethylene molar ratio be 50% vinyl polybutadiene, 300 grams, weight percent is 5% to take by weighing Viscoat 295 150 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 180 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 220 ℃, and three Heating Zone Temperature are set at 220 ℃, and four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1
Embodiment 31
Be 95% to take by weighing polypropylene 2850 gram by weight percentage, weight percent is that 2% to take by weighing the contents of ethylene molar ratio be 91% vinyl polybutadiene, 60 grams, weight percent is 3% to take by weighing 1,6-hexanediyl ester 90 grams, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, and wherein a Heating Zone Temperature is set at 200 ℃, and two Heating Zone Temperature are set at 220 ℃, three Heating Zone Temperature are set at 220 ℃, four Heating Zone Temperature are set at 210 ℃, and extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1
Embodiment 32
Be 70% to take by weighing polypropylene 2100 gram by weight percentage, weight percent is that 29.9% to take by weighing the contents of ethylene molar ratio be 91% vinyl polybutadiene, 897 grams, weight percent is 0.1% to take by weighing Viscoat 295 3 gram, in stirrer behind the uniform mixing 20min, join L/D=40, Φ is in the twin screw extruder of 35mm, the revolution of forcing machine is set at 200 rev/mins, forcing machine is divided into four heating zone, wherein a Heating Zone Temperature is set at 200 ℃, two Heating Zone Temperature are set at 220 ℃, three Heating Zone Temperature are set at 220 ℃, four Heating Zone Temperature are set at 210 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table 1
The test result of table 1 embodiment 1～32
| Sequence number | Tensile strength (MPa) | Tensile modulus (MPa) | Elongation at break (%) | Tc (℃) | Melting index (g/10min) | Melt strength (cN) |
| Virgin pp | 38 | 700 | 762 | 110 | 2.28 | 5 |
| Embodiment 1 | 38 | 720 | 701 | 111 | 2.07 | 8 |
| Embodiment 2 | 38 | 744 | 690 | 113 | 1.78 | 11 |
| Embodiment 3 | 39 | 790 | 670 | 118 | 1.51 | 20 |
| Embodiment 4 | 38 | 750 | 680 | 114 | 1.71 | 13 |
| Embodiment 5 | 39 | 812 | 662 | 124 | 0.66 | 31 |
| Embodiment 6 | 39 | 781 | 672 | 117 | 1.65 | 16 |
| Embodiment 7 | 40 | 823 | 659 | 120 | 1.14 | 25 |
| Embodiment 8 | 40 | 832 | 641 | 127 | 0.41 | 42 |
| Embodiment 9 | 39 | 811 | 660 | 125 | 0.56 | 35 |
| Embodiment 10 | 41 | 841 | 629 | 122 | 1.07 | 27 |
| Embodiment 11 | 41 | 804 | 671 | 123 | 0.69 | 30 |
| Embodiment 12 | 42 | 852 | 641 | 120 | 1.12 | 24 |
| Embodiment 13 | 40 | 833 | 640 | 124 | 0.60 | 32 |
| Embodiment 14 | 42 | 867 | 622 | 127 | 0.45 | 37 |
| Embodiment 15 | 42 | 871 | 619 | 119 | 1.33 | 22 |
| Embodiment 16 | 41 | 970 | 607 | 122 | 1.01 | 28 |
| Embodiment 17 | 41 | 710 | 708 | 123 | 0.70 | 30 |
| Embodiment 18 | 39 | 849 | 635 | 127 | 0.43 | 39 |
| Embodiment 19 | 39 | 801 | 680 | 124 | 0.57 | 33 |
| Embodiment 20 | 38 | 829 | 645 | 122 | 1.05 | 27 |
| Embodiment 21 | 39 | 805 | 673 | 124 | 0.66 | 31 |
| Embodiment 22 | 38 | 785 | 691 | 120 | 1.08 | 26 |
| Embodiment 23 | 38 | 766 | 692 | 119 | 1.41 | 21 |
| Embodiment 24 | 38 | 780 | 688 | 119 | 1.35 | 22 |
| Embodiment 25 | 37 | 791 | 675 | 123 | 0.71 | 30 |
| Embodiment 26 | 39 | 775 | 689 | 118 | 1.45 | 20 |
| Embodiment 27 | 38 | 740 | 691 | 120 | 1.30 | 23 |
| Embodiment 28 | 39 | 732 | 699 | 124 | 0.63 | 32 |
| Embodiment 29 | 38 | 710 | 703 | 122 | 0.72 | 29 |
| Embodiment 30 | 37 | 768 | 692 | 120 | 1.40 | 21 |
| Embodiment 31 | 39 | 822 | 655 | 123 | 0.67 | 30 |
| Embodiment 32 | 40 | 835 | 632 | 124 | 0.65 | 31 |
Claims (6)
1, high bath strength acrylic resin, it is made up of A component, B component and C component: wherein the weight percent of A component is 70%～99.8%, and the weight percent of B component is 0.1%～29.9%, and the weight percent of C component is 0.1%～25%;
Described A component is the ecosystem acrylic resin; The acrylic resin of ecosystem acrylic resin for not adding any auxiliary agent, coming out by direct production in the polymeric kettle;
The B component is 50%～98% vinyl polybutadiene for the contents of ethylene molar ratio;
The C component is an esters of acrylic acid: Viscoat 295, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295, trimethylolpropane trimethacrylate, glycerol propoxylate triacrylate, pentaerythritol triacrylate, 1,4-butylene glycol diacrylate or 1,6 hexanediol diacrylate;
2, high bath strength acrylic resin according to claim 1 is characterized in that, the scope of the weight percent of described B component is 0.1%～20%.
3, high bath strength acrylic resin according to claim 1 is characterized in that, the scope of the weight percent of described C component is 0.1%～10%.
5, high bath strength acrylic resin according to claim 1 is characterized in that, described B component is 70%～98% vinyl polybutadiene for selection contents of ethylene molar ratio.
6, the preparation method of high bath strength acrylic resin according to claim 1 is characterized in that, step and condition are:
Melting graft reaction equipment is chosen twin screw extruder or single screw extrusion machine; With the A component, B component and C component mix by proportioning, join the material chamber from the spout of twin screw extruder or single screw extrusion machine, carry out melting graft reaction, twin screw extruder or single screw extrusion machine revolution are set at 20 rev/mins～300 rev/mins, it is four heating zone that twin screw extruder or single screw extrusion machine are divided into, wherein, one Heating Zone Temperature is set at 190 ℃～230 ℃, two Heating Zone Temperature are set at 200 ℃～240 ℃, three Heating Zone Temperature are set at 200 ℃～240 ℃, four Heating Zone Temperature are set at 200 ℃～240 ℃, and extruding pelletization obtains high bath strength acrylic resin.
7, the preparation method of high bath strength acrylic resin according to claim 1 is characterized in that, step and condition are:
Melting graft reaction equipment is chosen Banbury mixer; A component, B component and C component are mixed by proportioning, join the material chamber, carry out melting graft reaction from the spout of Banbury mixer, temperature of reaction is set at 190 ℃～240 ℃, reaction times is 1～15 minute, finishes reaction, obtains high bath strength acrylic resin.
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| CN102372889A (en) * | 2010-08-13 | 2012-03-14 | 十堰飞纳科科技有限公司 | High toughness and high rigidity polypropylene nano-composite material, and preparation method thereof |
| CN102030960B (en) * | 2010-12-31 | 2013-03-13 | 浙江大学 | Preparation method of high-melt-strength polyolefine comprising hybrid long branch-chain structure |
| CN104610506A (en) * | 2015-01-04 | 2015-05-13 | 南通日之升高分子新材料科技有限公司 | High-melt strength polypropylene and preparation method thereof |
| CN113174006A (en) * | 2021-03-11 | 2021-07-27 | 常州都铂高分子有限公司 | Method for preventing gelation and large particle generation of resin |
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| CN1223678A (en) * | 1996-06-24 | 1999-07-21 | 阿克佐诺贝尔公司 | Process for enhancing the melt strength of polypropylene (CO) polymers |
| CN1432584A (en) * | 2002-01-17 | 2003-07-30 | 扬子石油化工股份有限公司 | Method of increasing melt strength of polypropylene |
| US6646019B2 (en) * | 2000-06-23 | 2003-11-11 | 3M Innovative Properties Company | Fibrillated foam article |
| US20040127649A1 (en) * | 2002-10-24 | 2004-07-01 | Palanisamy Arjunan | Branched crystalline polypropylene |
| CN1775851A (en) * | 2005-11-25 | 2006-05-24 | 中山大学 | High Melt strength polypropylene resin and its preparing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1223678A (en) * | 1996-06-24 | 1999-07-21 | 阿克佐诺贝尔公司 | Process for enhancing the melt strength of polypropylene (CO) polymers |
| US6646019B2 (en) * | 2000-06-23 | 2003-11-11 | 3M Innovative Properties Company | Fibrillated foam article |
| CN1432584A (en) * | 2002-01-17 | 2003-07-30 | 扬子石油化工股份有限公司 | Method of increasing melt strength of polypropylene |
| US20040127649A1 (en) * | 2002-10-24 | 2004-07-01 | Palanisamy Arjunan | Branched crystalline polypropylene |
| CN1775851A (en) * | 2005-11-25 | 2006-05-24 | 中山大学 | High Melt strength polypropylene resin and its preparing method |
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