CN103146161B - A kind of modified polylactic resin composition and method of making the same and application - Google Patents
A kind of modified polylactic resin composition and method of making the same and application Download PDFInfo
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Abstract
The present invention relates to a kind of modified polylactic resin composition and method of making the same and application, belong to technical field of polymer materials.Solve the existing technical problem that simultaneously can not realize high tenacity, high heat resistance and flame retardant resistance, provide a kind of modified polylactic resin composition to comprise the weight part of following composition: poly(lactic acid): 50 ~ 90; Toughner: 1.0 ~ 15; Nucleator: 0.5 ~ 15 part; Fire retardant: 1.0 ~ 25.Meanwhile, present invention also offers the preparation method of this modified polylactic resin composition, comprise and poly(lactic acid), toughner, nucleator and fire retardant are mixed according to the above ratio, then, carry out extruding pelletization in the molten state, obtain modified polylactic resin composition.Product of the present invention has high tenacity, high heat resistance and high flame retardant and good processing characteristics concurrently, can be applied to engineering plastics; And technological process of the present invention simplifies, working (machining) efficiency is high, easy handling and production cost low.
Description
Technical field
The present invention relates to a kind of modified polylactic resin composition and method of making the same and application, belong to technical field of polymer materials.
Background technology
Poly(lactic acid) is a kind of biodegradable resin, and it take lactic acid as monomer, and form by lactic acid polycondensation or by the dimer-rac-Lactide ring-opening polymerization of lactic acid, poly(lactic acid) has good Biodegradable.
Poly(lactic acid) (PLA) is the maximum degradable plastic product of output, has higher mechanical strength, but toughness and thermotolerance poor, the modification therefore for poly(lactic acid) toughness and thermotolerance aspect is more.Through to toughness and thermotolerance aspect modified, the comprehensive mechanical property of poly(lactic acid) is obviously promoted, and has the potentiality as engineering plastics, as small household appliance casing moulding etc.And as engineering plastics use, require that material has certain flame retardant properties, therefore, for poly(lactic acid) engineering plastics field should be used for say, should keep high strength prerequisite under, in toughness, thermotolerance and flame retardant resistance three aspect comprehensively modifying.But, in prior art for the modification of poly(lactic acid) often only for the improvement of single performance.As separately carried out modification to toughness, carry out modification to thermotolerance or carry out modification to flame retardant resistance separately separately.In addition, the modification patent that toughness and thermotolerance combine also is had been reported.As Chinese patent application (publication number: CN101914274A) discloses a kind of complete biodegradable transparent high-toughness polylactic acid resin and preparation method, by poly(lactic acid) and poly-1,2-monobehenate and the mixing of other auxiliary agent, adopt suitable working method, can obtain super tough poly(lactic acid).
And for example Chinese patent application (publication number: CN101337416A) discloses a kind of manufacture method of heat-proof polylactic acid ejection formed piece, mixture injection moulding in injection moulding machine of poly(lactic acid) and nucleation is obtained work in-process, then by work in-process anneal under proper temperature, make crystallization of polylactic acid resin completely thus increase thermotolerance.
And for example Chinese patent application (publication number: CN102924892A) discloses a kind of high heat-resisting high-toughness polylactic acid resin composition and method of making the same, poly-L-lactic acid homopolymer containing 50 ~ 99.5 weight fraction in 100 weight part polylactic acid resin compositions, 0.5 ~ 50 weight part gathers D lactic acid copolymer, described poly-D lactic acid copolymer is prepared by gathering D lactic acid and second component and is obtained, second component is the polymkeric substance with flexible chain structure, has higher thermotolerance and toughness.
Comparatively speaking, the research flame-retardant modified to poly(lactic acid) is less, and the patent taking into account the flame-proof polylactic acid of toughness and thermotolerance is more rare.As Chinese patent application (publication number: CN101337416A) discloses a kind of toughened halogen-free flame-retardant polylactic acid blending material, while adding fire retardant, add appropriate toughner, obtain the poly(lactic acid) flame retardant products with improvement toughness.
As can be seen from above prior art, for poly(lactic acid) engineering plastics field should be used for say, unavoidable problem for toughness, thermotolerance and flame retardant resistance, but mostly concentrate on certain single performance in prior art or two performances carry out modification, for have concurrently simultaneously high tenacity, high heat resistance and high flame retardant three the aspect work of carrying out comprehensive modification seldom mention, also not mentioned fire retardant is on the impact of toughness and thermotolerance.As Chinese patent application (publication number: CN101787185A) discloses a kind of heat-proof polylactic acid fire retardant material, in poly(lactic acid), add polycarbonate, aliphatic polyester, linking agent, the auxiliary agent mixing such as halogen-free flame retardants, resulting materials has thermotolerance, flame retardant resistance and higher toughness.But be added with non-degradable resin polycarbonate in this blend, affect the degradation property of poly(lactic acid).
Summary of the invention
The present invention is directed to above problems of the prior art, a kind of modified polylactic resin composition and method of making the same and application are provided.The technique effect having high tenacity, high heat resistance and high flame retardant concurrently can be realized.
An object of the present invention is achieved by the following technical programs, a kind of modified polylactic resin composition, and said composition comprises the weight part of following composition:
Poly(lactic acid): 50 ~ 90; Toughner: 1.0 ~ 15; Nucleator: 0.5 ~ 15 part; Fire retardant: 1.0 ~ 25;
Described toughner is for having flexible biodegradable polymkeric substance; Described fire retardant is selected from one or more in the multipolymer of nitrogenous flame ratardant, phosphonium flame retardant, the fire retardant of phosphorous and nitrogen, esters of acrylic acid and type siloxane; Described modified polylactic resin composition has toughness, thermotolerance and flame retardant resistance concurrently.
Modified polylactic resin composition of the present invention take poly(lactic acid) as matrix resin, and by adding toughner, nucleator and fire retardant in matrix polylactic resin, the amount that one side adds due to toughner is too much, and thermotolerance can be made to decline.On the other hand, adding toughner increases while toughness, and the flame retardant properties of material can be made again to decline, and fire retardant add the thermotolerance and toughness that can affect material.Therefore, the present invention is by the composition between each material of control and content, material is made to play synergy each other, thus realize the modified polylactic resin composition having toughness, thermotolerance and flame retardant resistance concurrently, and modified polylactic resin composition of the present invention does not need to add the degradation property that nondegradable polycarbonate can not affect material.Therefore, modified polylactic resin combination of the present invention can realize the effect having toughness, thermotolerance and flame retardant resistance concurrently, and can also ensure that product has good degradation rate, the organic polymer part in goods can be degradable.
In above-mentioned modified polylactic resin composition, as preferably, described modified polylactic resin composition comprises the weight part of following composition:
Poly(lactic acid): 70 ~ 80; Toughner: 5.0 ~ 10; Nucleator: 2.0 ~ 10 parts; Fire retardant: 5.0 ~ 15.
In above-mentioned modified polylactic resin composition, by research, the present invention finds that the toughness of branched polylactic acid is higher than line style poly(lactic acid), but the too high degree of branching can affect crystallization rate and the degree of crystallinity of poly(lactic acid).But degree of crystallinity change has impact greatly to the thermotolerance of material and toughness, the increase of degree of crystallinity makes the toughness of material reduce, and the problem that thermotolerance increases; Degree of crystallinity reduces the problem that can make again toughness of material increase and thermotolerance reduction, thus causes there is thermotolerance increase and toughness reduces or thermotolerance reduces and the problem of toughness increase.As preferably, the degree of branching of described poly(lactic acid) is 1 ~ 12.As further preferred, the degree of branching of described poly(lactic acid) is 3 ~ 6.
In above-mentioned modified polylactic resin composition, as preferably, described in there are one or more that flexible biodegradable polymkeric substance is selected from toughner B1, toughner B2, toughner B3 or toughner B4.Wherein, the structural formula of described toughner B1 is as follows:
In formula, x is selected from the integer of 2 ~ 6, and y is selected from the integer of 1 ~ 6, and preferred x, y are independently selected from the integer of 3 ~ 5 separately; N is selected from the integer of 500 ~ 3000.Described toughner B1 is by a kind of diprotic acid and a kind of dibasic alcohol simple linear polymer by polycondensation copolymerization.As further preferred, described toughner B1 is selected from one or more in poly butylene succinate, poly-adipic acid butanediol ester, polyethylene glycol succinate.Such toughner is degradable, has the polyester material of flexible molecule chain, good with the consistency of poly(lactic acid), plays good toughening effect simultaneously.Further preferred, described toughner B1 is poly butylene succinate, and its number-average molecular weight is 1 × 10
4~ 5 × 10
5.Preferably, the number-average molecular weight of described poly butylene succinate is 1 × 10
4~ 1.5 × 10
5.
The structural formula of described toughner B2 is as follows:
X in formula
1, z
1independently be selected from the integer of 2 ~ 6 separately; y
1, p
1independently be selected from the integer of 1 ~ 6 separately; n
1, m
1independently be selected from the integer of 20 ~ 1500 separately.The polymkeric substance that described toughner B2 is obtained by multiple diprotic acid and multiple diol copolymer, specifically comprise adipic acid-co-butyleneglycol-co-terephthaldehyde acid copolymer, adipic acid-co-butyleneglycol-co-succinic acid multipolymer, and the number-average molecular weight of polymkeric substance is 1 × 10
4~ 5 × 10
5.
The structural formula of described toughner B3 is as follows:
X in formula
2be the integer of 2 ~ 6, be preferably the integer of 4 ~ 5; n
2it is the integer of 100 ~ 5000.Described toughner B3 is the polymkeric substance obtained by lactone ring opening polymerization.As preferably, described toughner B3 is pla-pcl, and the number-average molecular weight of polymkeric substance is 1 × 10
4~ 5 × 10
5.Degradability is good, has the polyphosphazene polymer ester material of long flexible chain structure, adds this small amount of polyester and can reach good toughening effect in polylactic acid based resin.
One of the structural formula of described toughner B4 is following:
N in formula
3, m
3independently be selected from the integer of 100 ~ 500 separately, r is selected from the integer of 300 ~ 1000.As preferably, described toughner B4 is selected from vinylbenzene-co-hydrogenated butadiene-co-styrol copolymer, styrene-co-butadiene-co-styrol copolymer, styrene-co-isoprene-co-styrol copolymer.Above-mentioned toughner is thermoplastic elastomer, effectively can increase the toughness of poly(lactic acid).
In above-mentioned modified polylactic resin composition, as preferably, described fire retardant at least comprises the multipolymer of esters of acrylic acid and siloxanes, and its structural formula is as follows:
In formula, * is radical initiator; R
1and R
2independently be selected from C separately
1~ C
4alkyl, as methyl, ethyl, sec.-propyl, butyl etc.; R
3and R
4the phenyl be independently selected from separately phenyl, replacing containing alkyl or C
1~ C
6alkyl in one, described C
1~ C
6alkyl as methyl, ethyl, base, sec.-propyl etc.; Described n
4be the integer of 70 ~ 1000, m
4it is the integer of 50 ~ 500.As preferably, described radical initiator is the radical initiator that acrylic ester high molecular type material is conventional, and described radical initiator is as Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO), dicumyl peroxide (DCP) etc.This fire retardant can improve Drawing abillity and resistance toheat, thus further solve because adding the thermotolerance of toughner on material and the impact of flame retardant resistance, while realizing increasing modified polylactic resin composition flame retardant resistance, can ensure again to increase composition toughness and resistance toheat simultaneously.This multipolymer and fire retardant of the present invention with the use of, especially phosphorus flame retardant with the use of, beyond thought flame retardant effect can be reached, over-all properties can be had concurrently simultaneously and be effectively improved.
In above-mentioned modified polylactic resin composition, as preferably, described nitrogenous flame ratardant is selected from one or more in trimeric cyanamide urea hydrochlorate, trimeric cyanamide, poly-isocyanurate or isocyanuric acid ester.Described phosphonium flame retardant is selected from one or more in red phosphorus, Tritolyl Phosphate, triphenyl phosphonates, Resorcinol two banks fat, dihydroxyphenyl propane two (phenylbenzene) phosphonates or dihydroxyphenyl propane two (dimethyl) phosphonates.Described nitrogenous and phosphorus fire retardant is selected from one or more in polyphosphoric acid amine, melamine phosphoric acid salt, melamine pyrophosphate salt or melamine poly-phosphate.The acrylate section of the multipolymer of described acrylate and siloxanes and the number-average molecular weight of siloxanes section are independently 1 × 10 separately
4~ 5 × 10
5.
In above-mentioned modified polylactic resin composition, as preferably, described nucleator is selected from one or more in talcum powder, wollastonite, calcium sulfate crystal whiskers or silicon carbide whisker, and the length-to-diameter ratio of described nucleator is 5:1 ~ 15:1, and described length-to-diameter ratio is preferably 8:1 ~ 10:1.If length-to-diameter ratio is lower than 5:1, then nucleating effect is poor; If more than 15:1, then easily to fracture in melt blending process, nucleating effect can be made equally poor.Nucleator has material impact to the heat-resisting effect improving poly(lactic acid), if polylactic acid crystal degree is low, heat resisting temperature can be made also low.The nucleator that efficiency is high in the degree of crystallinity of raising of shorter time poly(lactic acid), thus can significantly improve its thermotolerance, enhances productivity simultaneously.As preferably, described nucleator is talcum powder.As further preferred, the order number of described nucleator is greater than 1500 orders, is preferably 2500 ~ 5000 orders.If order number is lower than 1500 orders, then nucleating effect is poor; If order number is higher than 5000 orders, be then unfavorable for the dispersion of nucleator in polylactic resin.
In above-mentioned modified polylactic resin composition, as preferably, described poly(lactic acid) is poly-L-lactic acid.Further preferably, the degree of branching of described poly-L-lactic acid is 1 ~ 12, be preferably 1 ~ 6, and number-average molecular weight is 1 × 10
4~ 5 × 10
5.
The preparation method of above-mentioned modified polylactic resin composition of the present invention adopts the method for this area routine to realize, and also without the need to adopting special equipment, is conducive to industrialized production.
Two of object of the present invention is achieved by the following technical programs, a kind of preparation method of modified polylactic resin composition, and the method comprises the following steps:
Poly(lactic acid), toughner, nucleator and fire retardant are mixed according to the above ratio, then, carries out extruding pelletization in the molten state, obtain modified polylactic resin composition.
In the preparation method of above-mentioned modified polylactic resin composition, described modified polylactic resin composition makes corresponding goods further, be filled in mould by the modified polylactic resin composition after granulation and carry out injection moulding and make corresponding goods, and the temperature of described mould is 70 DEG C ~ 120 DEG C.As further preferred, the temperature of described mould is 80 DEG C ~ 100 DEG C.Die temperature has important impact to polylactic acid crystal, and suitable die temperature can make polylactic acid melt at the interval sufficient crystallising of last Tc, while enhancing productivity, ensures the object that poly(lactic acid) thermotolerance is high.
Three of object of the present invention is achieved by the following technical programs: a kind of application of modified polylactic resin composition, and described modified polylactic resin composition is used for plastics.Because modified polylactic resin composition of the present invention has high tenacity, high heat resistance and high flame retardant concurrently, and there is higher degradation property, can apply widely and make engineering plastics, Some substitute ABS, HIPS, PBT etc.
In sum, the present invention compared with prior art, has the following advantages:
1. modified polylactic resin composition of the present invention has high tenacity, high heat resistance and high flame retardant and good processing characteristics concurrently, the vicat softening temperature of modified polylactic resin composition of the present invention reaches more than 94 DEG C, flame retardant resistance can reach UL-94V0 level, and original mechanical strength performance can be kept, and superior performance falls in the solution of material, the organic polymer part in material can be degradable.
2. modified polylactic resin composition of the present invention passes through the selection of the poly(lactic acid) degree of branching and the multipolymer of preferred fire retardant esters of acrylic acid and type siloxane copolymerization, can better realize performance of the present invention, ensure high tenacity, high flame retardant and high heat resistance, and the over-all properties of product is more superior.
3. the preparation method of modified polylactic resin composition of the present invention, has that technological process simplifies, high, the easy handling of working (machining) efficiency and a low advantage of production cost.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail, but the present invention is not limited to these embodiments.
Embodiment 1
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 75 parts, number-average molecular weight is 1 × 10
5;
Toughner: 10 parts, described toughner is poly butylene succinate, and its number-average molecular weight is 8 × 10
4;
Nucleator: 5 parts, described nucleator is talcum powder, and its order number is 2500 orders;
Fire retardant: 10 parts, be specially the multipolymer 2 parts that described fire retardant is melamine cyanurate 8 parts and fire retardant esters of acrylic acid and silazane, the number-average molecular weight of acrylate section and siloxanes section is all about 5 × 10
4.
The preparation method of above-mentioned modified polylactic resin composition preferably adopts following methods to prepare:
Poly(lactic acid) 75 weight part is taken, its number-average molecular weight 1 × 10 according to the ratio of above-mentioned modified polylactic resin composition
5, toughner B1 poly butylene succinate 10 weight part, its number-average molecular weight 8 × 10
4, nucleator C talcum powder 5 weight part, its order number is 2500 orders, multipolymer 2 weight part of flame-retardants melamine cyanurate 8 weight part and fire retardant acrylate and siloxanes, and wherein each hop count average molecular weight of acrylate section and siloxanes section is all about 5 × 10
4.Add in stirrer and carry out premix evenly, then add extruding pelletization in twin screw extruder, in twin screw extruder, each section of temperature setting is respectively 150 DEG C from opening for feed to discharge port, 180 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 185 DEG C, obtain polydactyl acid composition.Can further the polydactyl acid composition after granulation be put into mould and carry out injection moulding at injection moulding machine, injection moulding machine each section of temperature setting is 150 DEG C from opening for feed to discharge port, 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, keep die temperature at 80 DEG C ~ 100 DEG C, obtain corresponding product material.
Embodiment 2
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 70 parts, number-average molecular weight 1 × 10
4;
Toughner: 10 weight parts, described toughner is hexanodioic acid-co-butyleneglycol-co-succinic acid multipolymer, and number-average molecular weight is 9 × 10
4;
Nucleator: 5 weight parts, described nucleator is calcium sulfate crystal whiskers, and order number is 2000 orders;
Fire retardant: 15 weight parts, described fire retardant is multipolymer 3 weight part of Tritolyl Phosphate 12 weight part and fire retardant esters of acrylic acid and siloxanes, and each hop count average molecular weight of acrylate section and siloxanes section is all about 5 × 10
4.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 3
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 70 weight parts, number-average molecular weight is 5 × 10
5;
Toughner B2 hexanodioic acid-co-butyleneglycol-co-succinic acid multipolymer: 5 weight parts, and number-average molecular weight 9 × 10
4;
Toughner B3 polycaprolactone: 5 weight parts, number-average molecular weight 7.5 × 10
4;
Nucleator: 5 weight parts, described nucleator is wollastonite, and order number is 3000 orders;
Flame-retardants melamine cyanurate: 8 weight parts;
Fire retardant Tritolyl Phosphate: 5 weight parts;
Multipolymer 2 weight part of fire retardant esters of acrylic acid and siloxanes, each hop count average molecular weight of acrylate section and siloxanes section is 5 × 10
4.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 4
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 70 weight parts, the degree of branching is 3, and number-average molecular weight 1 × 10
5;
Toughner B2 hexanodioic acid-co-butyleneglycol-co-succinic acid multipolymer: 5 weight parts, and number-average molecular weight 9 × 10
4;
Toughner B4SEBS(vinylbenzene-co-ethene-co-butylene-co-styrene block copolymer): 5 weight parts, and number-average molecular weight is 7.5 × 10
4;
Nucleator: 5 weight parts, described nucleator is magnesia crystal whisker, and order number is 2000 orders;
Flame-retardants melamine cyanurate: 10 weight parts;
Fire retardant polyphosphoric acid amine: 10 weight parts.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 5
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 50 weight parts, the degree of branching is 12, and number-average molecular weight 1 × 10
4;
Toughner B2 hexanodioic acid-co-butyleneglycol-co-succinic acid multipolymer: 3 weight parts, number-average molecular weight 5 × 10
5;
Toughner B4SEBS(vinylbenzene-co-ethene-co-butylene-co-styrene block copolymer): 2 weight parts, number-average molecular weight is 5 × 10
5;
Nucleator: 10 weight parts, described nucleator is silicon carbide whisker, and order number is 2000 orders, and the length-to-diameter ratio of described silicon carbide whisker is 5:1;
Fire retardant poly-isocyanurate: 2 weight parts;
Combustion inhibitor bisphenol A bis two (phenylbenzene) phosphonates: 3 weight parts.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 6
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 50 weight parts, number-average molecular weight 1 × 10
4;
Toughner B2 adipic acid-co-butyleneglycol-co-terephthaldehyde acid copolymer: 10 weight parts, number-average molecular weight 1 × 10
4;
Toughner B4 vinylbenzene-co-hydrogenated butadiene-co-styrol copolymer: 5 weight parts, number-average molecular weight is 5 × 10
5;
Nucleator: 15 weight parts, described nucleator is calcium sulfate crystal whiskers, and order number is 2500 orders, and the length-to-diameter ratio of described calcium sulfate crystal whiskers is 15:1;
Flame-retardants melamine urea hydrochlorate: 5 weight parts;
Combustion inhibitor bisphenol A bis two (dimethyl) phosphonates: 20 weight parts.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 7
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 50 weight parts, the degree of branching of poly-L-lactic acid is 3, and number-average molecular weight is 5 × 10
5;
Toughner B4 styrene-co-isoprene-co-styrol copolymer: 10 weight parts, number-average molecular weight is 1 × 10
4;
Nucleator: 15 weight parts, described nucleator is talcum powder, and order number is 2500 orders, and described talcous length-to-diameter ratio is 10:1;
Copolymer 15 weight part of fire retardant esters of acrylic acid and siloxanes, and each hop count average molecular weight of esters of acrylic acid section and type siloxane section is all about 1 × 10
5.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 8
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 80 weight parts, the degree of branching of poly-L-lactic acid is 12, and number-average molecular weight is 1 × 10
4;
Toughner B1 poly butylene succinate: 10 weight parts, number-average molecular weight is 5 × 10
5;
Nucleator: 2 weight parts, described nucleator is silicon carbide, and order number is 5000 orders, and the length-to-diameter ratio of described silicon carbide is 8:1;
Multipolymer 5 weight part of fire retardant esters of acrylic acid and type siloxane, and each hop count average molecular weight of esters of acrylic acid section and type siloxane section is all about 5 × 10
5.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 9
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 75 weight parts, the degree of branching of poly-L-lactic acid is 6, and number-average molecular weight is 8 × 10
4;
Toughner B1 poly butylene succinate: 15 weight parts;
Nucleator: 5 weight parts, described nucleator is talcum powder, and order number is 2500 orders;
Copolymer 10 weight part of fire retardant esters of acrylic acid and type siloxane, and each hop count average molecular weight of acrylate section and siloxanes section is all about 5 × 10
5.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 10
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 75 weight parts, the degree of branching of poly-L-lactic acid is 6, and number-average molecular weight is 1 × 10
4;
Toughner B1 polyethylene glycol succinate: 10 weight parts;
Nucleator: 5 weight parts, described nucleator is talcum powder, and order number is 5000 orders;
Fire retardant: 5 weight parts, described fire retardant is melamine phosphoric acid salt;
Copolymer 10 weight part of fire retardant esters of acrylic acid and type siloxane, each hop count average molecular weight of acrylate section and siloxanes section is 5 × 10
5.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 11
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 75 weight parts, the degree of branching of poly-L-lactic acid is 5, and number-average molecular weight is 1 × 10
5;
Toughner B1 gathers adipic acid butanediol ester: 15 weight parts;
Nucleator: 5 weight parts, described nucleator is talcum powder, and order number is 3000 orders;
Fire retardant melamine phosphoric acid salt: 5 weight parts;
Fire retardant poly-isocyanurate: 5 weight parts;
Multipolymer 5 weight part of fire retardant esters of acrylic acid and siloxanes, and each hop count average molecular weight of esters of acrylic acid section and type siloxane section is 1 × 10
4.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 12
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 75 weight parts, the degree of branching of poly-L-lactic acid is 6, and number-average molecular weight is 1 × 10
4;
Toughner B1 poly butylene succinate: 15 weight parts;
Nucleator: 5 weight parts, described nucleator is talcum powder, and order number is 1500 orders;
Combustion inhibitor bisphenol A bis two (phenylbenzene) phosphonates: 5 weight parts;
Copolymer 10 weight part of fire retardant esters of acrylic acid and type siloxane, its structural formula is as follows:
In formula, * is radical initiator; Described radical initiator is selected from one of Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO), dicumyl peroxide (DCP); Described R
1and R
2independently be selected from C separately
1~ C
4alkyl, described R
1and R
2independently be preferably the one in methyl, ethyl separately; R
3and R
4the phenyl be independently selected from separately phenyl, replacing containing alkyl or C
1~ C
6alkyl in one, be preferably ethyl; Described n
4be the integer of 70 ~ 1000, m
4be the integer of 50 ~ 500, preferably, described n
4be the integer of 500 ~ 800, m
4it is the integer of 100 ~ 300.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 13
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 75 weight parts, the degree of branching of poly-L-lactic acid is 3, and number-average molecular weight is 1 × 10
4;
Toughner B1:12 weight part; The structural formula of toughner B1 is as follows:
In its Chinese style, x is 2, y is 6, and n is 500 ~ 700; Or x is 3, y is 5, and n is 2000 ~ 2500; Or x is 6, y is 1, and n is 2500 ~ 3000;
Nucleator: 5 weight parts, described nucleator is talcum powder, and order number is 1500 orders, and length-to-diameter ratio is 9:1;
Combustion inhibitor bisphenol A bis two (phenylbenzene) phosphonates: 5 weight parts;
Copolymer 10 weight part of fire retardant butyl acrylate and siloxanes, its structural formula is as follows:
In formula, * is radical initiator, and described radical initiator is Diisopropyl azodicarboxylate (AIBN); R
1for H, R
2for methyl; R
3and R
4be methyl; And the number-average molecular weight of butyl acrylate section and dimethyl siloxane section is about 2 × 10 respectively
4with 4 × 10
4.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 14
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 50 weight parts, the degree of branching is 1, number-average molecular weight 1 × 10
4;
Toughner B2:10 weight part, the structural formula of toughner B2 is as follows:
X in formula
1, z
1be integer 2, y
1, p
1be 6, n
1be 20, m
1be 1500; Or x
1, z
1be integer 6, y
1, p
1be 2, n
1be 1500, m
1be 20;
Toughner B4 vinylbenzene-co-hydrogenated butadiene-co-styrol copolymer: 5 weight parts, polymerization degree n
3, m
3being 100, r is 1000;
Nucleator: 15 weight parts, described nucleator is calcium sulfate crystal whiskers, and order number is 2000 orders, and the length-to-diameter ratio of described calcium sulfate crystal whiskers is 15:1;
Flame-retardants melamine urea hydrochlorate: 5 weight parts;
Combustion inhibitor bisphenol A bis two (dimethyl) phosphonates: 20 weight parts.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 15
A kind of modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 50 weight parts, number-average molecular weight 1 × 10
4;
Toughner B4 is selected from one of vinylbenzene-co-hydrogenated butadiene-co-styrol copolymer, styrene-co-butadiene-co-styrol copolymer, styrene-co-isoprene-co-styrol copolymer: 5 weight parts, polymerization degree n
3, m
3being 500, r is 300;
Nucleator: 15 weight parts, described nucleator is calcium sulfate crystal whiskers, and order number is 2000 orders, and the length-to-diameter ratio of described calcium sulfate crystal whiskers is 15:1;
Flame-retardants melamine urea hydrochlorate: 5 weight parts;
Combustion inhibitor bisphenol A bis two (dimethyl) phosphonates: 20 weight parts.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Embodiment 16
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly(lactic acid): 70 weight parts, number-average molecular weight is 1 × 10
5;
Toughner B2 hexanodioic acid-co-butyleneglycol-co-succinic acid multipolymer: 5 weight parts, and number-average molecular weight 9 × 10
4;
Toughner B3:5 weight part, the structural formula of described toughner B3 is as follows:
X in formula
2be 2 or 4, n
2be 5000; Or x
2be 6 or 5, n
2be 100;
Nucleator: 5 weight parts, described nucleator is wollastonite, and order number is 3000 orders;
Flame-retardants melamine cyanurate: 8 weight parts;
Fire retardant Tritolyl Phosphate: 5 weight parts;
Multipolymer 2 weight part of fire retardant esters of acrylic acid and type siloxane, each hop count average molecular weight of esters of acrylic acid section and type siloxane section is 5 × 10
4.
Embodiment 17
Modified polylactic resin composition, described composition comprises the weight part of following composition:
Poly-L-lactic acid: 80 weight parts, the degree of branching is 6, and number-average molecular weight is 5.0 × 10
4;
Toughner B1 poly butylene succinate: 15 weight parts;
Nucleator: 5 weight parts, described nucleator is talcum powder, and order number is 1500 orders;
Combustion inhibitor bisphenol A bis two (phenylbenzene) phosphonates: 15 weight parts;
Copolymer 10 weight part of fire retardant β-dimethyl-aminoethylmethacrylate and Dimethicone Copolyol, wherein, the number-average molecular weight of β-dimethyl-aminoethylmethacrylate section and dimethyl siloxane section is respectively 5 × 10
4, 1 × 10
4.
Structure formula is as follows:
In formula, * is radical initiator; Described radical initiator is selected from one of Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO), dicumyl peroxide (DCP); Described R
1for methyl, R
2for ethyl; R
3and R
4be methyl; Described n
4be the integer of 400 ~ 500, m
4it is the integer of 50 ~ 100.
The preparation method of above-mentioned modified polylactic resin composition is consistent with the method described in embodiment 1, repeats no more here.
Comparative example 1
Be 1 × 10 by number-average molecular weight
5pure poly(lactic acid) 100 weight part add injection moulding in injection moulding machine, the setting of injection moulding machine each section of temperature is respectively 150 DEG C from opening for feed to discharge port, 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, keeps die temperature at 20 DEG C ~ 40 DEG C, obtains corresponding material.
Comparative example 2
Be 1 × 10 by number-average molecular weight
5poly(lactic acid): 75 weight parts, toughner B1 poly butylene succinate 25 weight part adds in stirrer that to carry out premix even, then extruding pelletization is carried out with in twin screw extruder, forcing machine each section of temperature setting is respectively 150 DEG C from opening for feed to discharge port, 180 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 185 DEG C.Modified particle after granulation is put into mould and is carried out injection moulding at injection moulding machine, and injection moulding machine each section of temperature setting is respectively 150 DEG C from opening for feed to discharge port, 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, keep die temperature at 20 DEG C ~ 40 DEG C, the corresponding material of gained.
Comparative example 3
By number-average molecular weight 1 × 10
5poly(lactic acid): 75 weight parts, toughner B1 poly butylene succinate 20 weight part, order number is 2500 object nucleator talcum powder 5 weight parts, join in stirrer that to carry out premix even, then in twin screw extruder, extruding pelletization is carried out, forcing machine each section of temperature setting is respectively 150 DEG C from opening for feed to discharge port, 180 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 185 DEG C, the injection moulding in injection moulding machine of modified particle after material will be made, injection moulding machine each section of temperature setting is respectively 150 DEG C from opening for feed to discharge port, 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, keep die temperature at 80 DEG C ~ 100 DEG C, obtain corresponding material.
Comparative example 4
Be 1 × 10 by number-average molecular weight
5poly(lactic acid) 75 weight part, it is even that flame-retardants melamine cyanurate 25 weight part adds premix in stirrer, then add in twin screw extruder and carry out extruding pelletization, forcing machine each section of temperature setting is respectively 150 DEG C from opening for feed to discharge port, 180 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 185 DEG C, carry out injection moulding by putting into mould after granulation at injection moulding machine, injection moulding machine each section of temperature setting is respectively 150 DEG C from opening for feed to discharge port, 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, keep die temperature at 20 DEG C ~ 40 DEG C, obtain corresponding material.
Random selecting above-described embodiment and compare according in the respective material that obtains carry out performance test, concrete test result is as with following table 1 and table 2.
Table 1:
Table 2:
As can be seen from above-mentioned table 1 and table 2, the present invention is through carrying out modification to polylactic resin, the modified polylactic resin material obtained, while the original mechanical strength performance of maintenance, achieves and has high tenacity (notched Izod impact strength) concurrently, high heat resistance (vicat softening temperature (B
50)) and the effect of high flame retardant, it can also be seen that from table 1 and table 2, modified polylactic resin composition of the present invention is not a kind of simple combination, has unforeseeable technique effect.Because modified polylactic resin composition of the present invention has high tenacity, high heat resistance and high flame retardant concurrently, therefore, modified polylactic resin combination of the present invention can obtain and apply to a certain extent in engineering plastics field.
Specific embodiment described in the present invention is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Although made a detailed description the present invention and quoted some specific embodiments as proof, to those skilled in the art, only otherwise it is obvious for leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (8)
1. a modified polylactic resin composition, is characterized in that, said composition comprises the weight part of following composition:
Poly(lactic acid): 50 ~ 90; Toughner: 1.0 ~ 15; Nucleator: 0.5 ~ 15 part; Fire retardant: 1.0 ~ 25;
Described toughner is for having flexible biodegradable polymkeric substance; Described fire retardant is selected from one or more in the multipolymer of nitrogenous flame ratardant, phosphonium flame retardant, the fire retardant of phosphorous and nitrogen, vinylformic acid acids and siloxanes; Described modified polylactic resin composition has toughness, thermotolerance and flame retardant resistance concurrently; The degree of branching of described poly(lactic acid) is 1 ~ 12, and described fire retardant at least comprises the multipolymer of esters of acrylic acid and siloxanes, and its structural formula is as follows:
In formula, * is radical initiator; R
1and R
2independently be selected from C separately
1~ C
4alkyl; R
3and R
4the phenyl be independently selected from separately phenyl, replacing containing alkyl or C
1~ C
6alkyl in one; Described n
4be the integer of 70 ~ 1000, m
2it is the integer of 50 ~ 500; In the multipolymer of described acrylate and siloxanes, the number-average molecular weight of acrylate section and siloxanes section is independently 1 × 10 separately
4~ 5 × 10
5.
2. modified polylactic resin composition according to claim 1, is characterized in that, described in there are one or more that flexible biodegradable polymkeric substance is selected from toughner B1, toughner B2, toughner B3 or toughner B4;
The structural formula of described toughner B1 is as follows:
In formula, x is selected from the integer of 2 ~ 6, and y is selected from the integer of 1 ~ 6; N is selected from the integer of 500 ~ 3000;
The structural formula of described toughner B2 is as follows:
X in formula
1, z
1independently be selected from the integer of 2 ~ 6 separately; y
1, p
1independently be selected from the integer of 1 ~ 6 separately; n
1, m
1independently be selected from the integer of 20 ~ 1500 separately;
The structural formula of described toughner B3 is as follows:
X in formula
2be the integer of 2 ~ 6, n
2it is the integer of 100 ~ 5000;
One of the structural formula of described toughner B4 is following:
N in formula
3, m
3independently be selected from the integer of 100 ~ 500 separately, r is selected from the integer of 300 ~ 1000.
3. modified polylactic resin composition according to claim 2, is characterized in that, described toughner B1 is selected from one or more in poly butylene succinate, poly-adipic acid butanediol ester, polyethylene glycol succinate; Described toughner B2 be selected from adipic acid-co-butyleneglycol-co-terephthaldehyde acid copolymer, adipic acid-co-butyleneglycol-co-succinic acid multipolymer one or both; Described toughner B3 is selected from pla-pcl; Described toughner B4 is selected from vinylbenzene-co-ethene-co-butylene-co-styrene block copolymer.
4. modified polylactic resin composition according to claim 1, is characterized in that, described nitrogenous flame ratardant is selected from one or more in trimeric cyanamide urea hydrochlorate, trimeric cyanamide, poly-isocyanurate or isocyanuric acid ester; Described phosphonium flame retardant is selected from one or more in red phosphorus, Tritolyl Phosphate, triphenyl phosphonates, Resorcinol two banks fat, dihydroxyphenyl propane two (phenylbenzene) phosphonates or dihydroxyphenyl propane two (dimethyl) phosphonates; Described nitrogenous and phosphorus fire retardant is selected from one or more in polyphosphoric acid amine, melamine phosphoric acid salt, melamine pyrophosphate salt or melamine poly-phosphate.
5. modified polylactic resin composition according to claim 1, is characterized in that, described nucleator is selected from one or more in talcum powder, wollastonite, calcium sulfate crystal whiskers or silicon carbide whisker, and the length-to-diameter ratio of described nucleator is 5:1 ~ 15:1.
6. the modified polylactic resin composition according to claim 1-2 any one, is characterized in that, described poly(lactic acid) is poly-L-lactic acid, and the degree of branching of described poly-L-lactic acid is 1 ~ 12, and number-average molecular weight is 1 × 10
4~ 5 × 10
5.
7. the preparation method of modified polylactic resin composition as described in claim 1-6 any one, it is characterized in that, described method comprises the following steps:
Poly(lactic acid), toughner, nucleator and fire retardant are mixed in proportion, then, carry out extruding pelletization in the molten state, obtain modified polylactic resin composition.
8. the application of modified polylactic resin composition as described in claim 1-6 any one, is characterized in that, described modified polylactic resin composition is used for plastics.
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| KR20160031609A (en) * | 2014-09-12 | 2016-03-23 | 한화토탈 주식회사 | Flame-retardant polylactic acid composition |
| CN105780189A (en) * | 2016-03-28 | 2016-07-20 | 桂林理工大学 | Preparation method of sisal cellulose nano-whisker enhanced polylactic acid/poly(ethylene succinate) biological composite material |
| CN107619585A (en) * | 2016-07-14 | 2018-01-23 | 中国科学院宁波材料技术与工程研究所 | The purposes of biological poly furandicarboxylic acid butanediol ester modified polylactic resin |
| CN106245147A (en) * | 2016-08-02 | 2016-12-21 | 长兴德诚纺织有限公司 | A kind of flame-proof polylactic acid fabric lining |
| CN109535673B (en) * | 2018-10-22 | 2021-05-25 | 诺思贝瑞新材料科技（苏州）有限公司 | Heat-resistant impact-resistant high-transparency polylactic acid composite material and preparation method thereof |
| CN109206871B (en) * | 2018-10-22 | 2021-05-25 | 四川大学 | Flame-retardant toughened biodegradable polylactic acid material and preparation method thereof |
| CN111363322B (en) * | 2018-12-26 | 2022-05-31 | 浙江海正生物材料股份有限公司 | Flame-retardant polylactic resin composition and preparation method thereof |
| GB2591121A (en) * | 2020-01-16 | 2021-07-21 | Floreon Transf Packaging Limited | Polylactic acid flame resistant blend |
| CN111235624B (en) * | 2020-01-19 | 2021-09-03 | 包头稀土研究院 | Lanthanum hydroxide nano whisker and preparation method and application thereof |
| CN112898749A (en) * | 2021-01-26 | 2021-06-04 | 苏州塑发生物材料有限公司 | Low-warpage high-toughness glass fiber reinforced polylactic acid composite material and preparation method thereof |
| CN112852131A (en) * | 2021-02-02 | 2021-05-28 | 苏州塑发生物材料有限公司 | High-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material and preparation method thereof |
| CN113381125B (en) * | 2021-07-13 | 2023-02-17 | 上海恩捷新材料科技有限公司 | Ion-conductive functional resin and lithium battery diaphragm containing same |
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