CN109517351A - A kind of high ductibility waterproof material and preparation method thereof - Google Patents
A kind of high ductibility waterproof material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high ductibility waterproof material and preparation method thereof, the raw material including following parts by weight: 120-160 parts of poly-lactic acid in high molecular weight, 40-65 parts of 196 unsaturated polyester resin, 10-22 parts of allyl compound, 6-15 parts of mica powder, 3-8 parts of ethyl hexyl ester of epoxidized soybean oil, 2-5 parts of fibrous talc, 1-3 parts of modification of chitosan, 3-10 parts of fatty alcohol polyoxyethylene ether, 0.02-0.13 parts of heat stabilizer, 80-110 parts of acetonitrile；Preparation method includes hybrid resin preparation, mixed glue solution preparation, the dry extrusion of mixing.Waterproof material of the invention, each materials compatibility is good, and the material processed has good ductility, shock resistance, is suitable as the waterproof material of roofworks.
Description
Technical field
The present invention relates to waterproof material technical fields, and in particular to a kind of high ductibility waterproof material and preparation method thereof.
Background technique
With the continuous improvement of living standards of the people and industrial level, people to the construction quality in room, building it is anti-
More stringent requirements are proposed for water leakproof, and the Innovation Input of water-proof building material also constantly increases, and technology innovation is accelerated.Existing
Waterproof leakproofing material mainly uses modified pitch rubber waterproof material in roofworks, but since it is easy aging, ductility and
The effect of permanent waterproof and anticorrosion is not achieved in poor fluidity, be easy to cause the leakage on roof, and maintenance cost is high.Some roofworkss
Aluminium sheet or stereotype are selected, due to lacking ductility, it is difficult to and the roofing to rise and fall is pasted closely.
Composite waterproof material currently used for roofworks is various in style, and it is big to be divided into four by its primary raw material formed
Class: pitch class, rubber plastic class, cement class, metal class.Due to most of composite material by high molecular polymer and additive,
Additive compound forms, and high molecular polymer itself has a good thermal stability, compressive property, but ductility and mobility compared with
Difference.
Polylactic acid is a kind of green thermoplastic polyester for integrating biological degradability, Bioabsorbable, is had good
Biocompatibility, degradability, tensile strength, compression modulus and hot formability, catabolite can penetrate into body metabolism, extensively
Applied to fields such as medical treatment, pharmacy, agriculturals, market prospects are extensive, can be used as the primary raw material of roof waterproof construction material.Mesh
Before, synthesis composite waterproof material is researched and developed using polylactic acid is primarily present following problems: (1) since it be hydrophobic material,
Elasticity and mobility are all to be improved, it usually needs change its elasticity and flowing using addition plasticizer, nano material etc.
Property, improve ductility；(2) chemical structure of polylactic acid lacks reactive functional groups, and degradation speed is fast, needs to be added auxiliary agent to subtract
Slow degradation speed, has certain difficulty of processing；(3) impact property of polylactic acid is poor, is undergoing after being prepared into roofing
After long-time thunderstorm or hail impact, surface folding is be easy to cause to be cracked.
Summary of the invention
In order to overcome above-mentioned technical problem, the purpose of the present invention is to provide a kind of high ductibility waterproof material and its systems
Polylactic acid and suberic acid are obtained poly-lactic acid in high molecular weight using melt-polycondensation, since poly-lactic acid in high molecular weight has by Preparation Method
The shock resistance that has lower molecular weight polylactic acid more excellent, elongation at break, it is changed with unsaturated polyester resin physics
Property after, enhance the mobility and ductility of polylactic acid on the basis of keeping mechanical performance, then pass through mixed sols preparation, mixed
The dry method squeezed out of material obtains the waterproof material, and each materials compatibility is good, the material processed have good ductility,
Shock resistance is suitable as the waterproof material of roofworks.
The purpose of the present invention can be achieved through the following technical solutions:
The present invention provides a kind of high ductibility waterproof material, the raw materials including following parts by weight: poly-lactic acid in high molecular weight
120-160 parts, 40-65 parts of 196 unsaturated polyester resin, 10-22 parts of allyl compound, 6-15 parts of mica powder, epoxy soybean
3-8 parts of oleic acid monooctyl ester, 2-5 parts of fibrous talc, 1-3 parts of modification of chitosan, 3-10 parts of fatty alcohol polyoxyethylene ether, heat are steady
Determine 0.02-0.13 parts of agent, 80-110 parts of acetonitrile；
The molecular weight of the poly-lactic acid in high molecular weight is 120000-150000, and preparation method includes the following steps:
1) it is added in three-necked flask after mixing 90% Pfansteihl and suberic acid according to mass ratio 60:1, access divides water
After device, condenser pipe, blender, p-methyl benzenesulfonic acid is added as catalyst, is warming up to 145 DEG C and is stirred to react, in time discharge point
Moisture in hydrophone；When generating there is no moisture, pressure in three-necked flask is reduced to 40-80Pa by the external vacuum pump of condenser pipe,
165 DEG C are warming up to, 18-22h is stirred to react, cooling obtains polylactic acid prepolymer；
2) polylactic acid prepolymer is added in reaction flask, epoxy resin is added after 180 DEG C of heating meltings, reaction flask is taken out true
Sky is poured out reactant and is cooled to room temperature, obtain poly-lactic acid in high molecular weight crude product when system starts solidification；
3) poly-lactic acid in high molecular weight crude product is ground into the slice that partial size is 6-10mm using pulverizer, reuses twin-screw
Extruder squeezes out to arrive the poly-lactic acid in high molecular weight in 180-220 DEG C.
High ductibility waterproof material of the invention chooses poly-lactic acid in high molecular weight and 196 unsaturated polyester resins as base
Body material.Due to only having the polylactic acid of higher molecular weight that just not only there is biocompatibility, degradability, also there is good machinery
Performance such as tensile strength, compression modulus, elongation at break, impact strength.Therefore, system of the present invention in poly-lactic acid in high molecular weight
In standby, using simple process, lower-cost direct melt polycondensation method compared with traditional polylactic acid ring-opening polymerisation method, first will
Pfansteihl and suberic acid generate the prepolymer of polylactic acid under the catalysis of p-methyl benzenesulfonic acid, then use epoxy resin as chain extension
The small molecules such as agent, lactic acid and lactic acid oligomer consume epoxy group and carry out chain extension, and finally squeezing out and obtaining molecular weight is 120000-
150000 poly-lactic acid in high molecular weight.196 unsaturated polyester resins are the linear unsaturated polyesters with a contracting ethanol modifier in benzene
Solution in ethylene is mixed with the linear macromolecule in poly-lactic acid in high molecular weight, will form fine and close macromolecules cross-linking structure, resistance
Every the entrance of molecule and dust, there is good water proof and dust proof performance.
The present invention is using ethyl hexyl ester of epoxidized soybean oil as environment-friendly plasticizer, and fatty alcohol polyoxyethylene ether is as nonionic
Surfactant, mica powder, fibrous talc are as inorganic filler.Specifically, ethyl hexyl ester of epoxidized soybean oil and high molecular weight
Polymer macromolecule in polylactic acid, 196 unsaturated polyester resins mutually improves polymer in the level of supramolecular structure
Mechanical property, ethyl hexyl ester of epoxidized soybean oil are distributed between the basic unit of supramolecular structure, promote the weight of polymeric matrix
Row, the ester group contained can be effectively reduced the glass transition temperature of polylactic acid, improve toughness；Partial size is lesser after polymer rearrangement
Mica powder, fibrous talc can be filled into the gap of derivatized polymers, form the fine and close reticular structure of arrangement,
On the basis of keeping toughness, due to mica powder, the temperature tolerance of fibrous talc, lubricity, so that the flowing of reticular structure
Property and elasticity are improved, and decrease the additive amount of polylactic acid, have saved cost；Since fatty alcohol polyoxyethylene ether is good
Good mobility can form polyacids-polyethers block copolymer with a part of polylactic acid, further improve dredging for the waterproof material
It is aqueous, and molecular weight is adjusted, alleviate degradation speed.
As a further solution of the present invention, the heat stabilizer is by (3,4-rthylene dioxythiophene monomer) polymer, mistake
After mixing according to mass ratio 1:0.5-0.8:0.01-0.02, ultrasonic 5min is filtered, vacuum degree 500- for potassium sulfate, ferric sulfate
Microwave drying obtains under 600Pa.
(the 3,4- ethene dioxythiophene list that heat stabilizer of the invention is simple with molecular structure, energy gap is small, conductivity is high
Body) polymer as main component, compounds with potassium peroxydisulfate, ferric sulfate, and it is environmentally protective, after being added to the waterproof material,
Not only there are good absorbent properties to ultraviolet light, additionally it is possible to which conductive, absorption electromagnetism increases the electromagnetic shielding of waterproof material and leads
Electrical property.
As a further solution of the present invention, the allyl compound be diallyl bisphenol, diallyl bisphenol S,
One of allyl phenoxy resin, diallyl diphenyl ether or a variety of combinations.
As a further solution of the present invention, in the preparation method of the poly-lactic acid in high molecular weight, to toluene in step 1)
The additive amount of sulfonic acid is the 0.1-0.3% of Pfansteihl quality；The molar ratio of polylactic acid prepolymer and epoxy resin is in step 2)
1.1-1.2:1。
As a further solution of the present invention, the modification of chitosan is hydroxypropyl chitosan, chitosan quaternary ammonium salt, carboxylic first
One of base chitosan quaternary ammonium salt or a variety of combinations.
The present invention also provides a kind of preparation methods of high ductibility waterproof material, comprising the following steps:
1) prepared by hybrid resin: weighing poly-lactic acid in high molecular weight, 196 unsaturated polyester resins according to parts by weight, is added anti-
It answers in device, is warming up to 120 DEG C of reaction 40-60min, stop heating, after temperature is reduced to 80 DEG C, it is aqueous to be concentrated under reduced pressure into system
Amount obtains hybrid resin less than 0.6%；
2) prepared by mixed glue solution: acetonitrile is fitted into separatory funnel, is slowly added dropwise into hybrid resin, cooperative mechanical stirring
It is completely dissolved hybrid resin, adds allyl compound, ethyl hexyl ester of epoxidized soybean oil, fatty alcohol polyoxyethylene ether, heat
Stabilizer, 40-60 DEG C of stirring obtain mixed glue solution to sticky glue shape；
3) mixing is dry squeezes out: mixed glue solution, mica powder, fibrous talc, modification of chitosan being uniformly mixed, put into
The mixture of partial size 6-10mm is ground into ball mill, mixture is squeezed in 85 DEG C of vacuum drying 6-8h by double screw extruder
It forms out；Wherein five areas, engine speed 200-400rpm are arranged in twin-screw extrusion, and subsidiary engine revolving speed is 10-20rpm.
As a further solution of the present invention, the temperature in five areas of the step 3) twin-screw extrusion is respectively as follows: an area
It is 160-170 DEG C, 2nd area are 170-175 DEG C, and 3rd area are 180-185 DEG C, and 4th area are 190-200 DEG C, and 5th area are 200-210 DEG C.
The preparation method of high ductibility waterproof material of the present invention, using first that poly-lactic acid in high molecular weight and 196 is unsaturated poly-
The heating of ester resin obtains hybrid resin after being concentrated under reduced pressure, then carries out the preparation of mixed glue solution, the dry extrusion of mixing, hybrid resin
Preparation process is conducive to the macromolecular structure that two kinds of polymer forms crosslinking, improves the shock resistance of polylactic acid；Mixed glue solution
In preparation process, acetonitrile all has good dissolubility as excellent solvent, to polarity and nonpolar molecule；It is squeezed in twin-screw
It is the optimum temperature selection obtained according to test of many times, so that the waterproof material squeezed out out in the temperature selection in five areas of machine
Good ductility and impact resistance can be played, the requirement of roof engineering material is met.
Beneficial effects of the present invention:
1, high ductibility waterproof material of the invention chooses poly-lactic acid in high molecular weight and 196 unsaturated polyester resin conducts
Basis material；Since the polylactic acid of higher molecular weight not only has biocompatibility, degradability, also there is good mechanical performance
Such as tensile strength, compression modulus, elongation at break, impact strength.196 unsaturated polyester resins, one contracting ethanol modifier
Solution of the linear unsaturated polyester in styrene, mixes with the linear macromolecule in poly-lactic acid in high molecular weight, will form densification
Macromolecules cross-linking structure, obstruct molecule and dust entrance so that preparation material have good waterproof anti-corrosion property
Energy.
2, the present invention is using ethyl hexyl ester of epoxidized soybean oil as environment-friendly plasticizer, ethyl hexyl ester of epoxidized soybean oil and high molecular weight
Polymer macromolecule in polylactic acid, 196 unsaturated polyester resins mutually improves polymer in the level of supramolecular structure
Mechanical property, ethyl hexyl ester of epoxidized soybean oil are distributed between the basic unit of supramolecular structure, promote the weight of polymeric matrix
Row, the ester group contained can be effectively reduced the glass transition temperature of polylactic acid, improve toughness；Partial size is lesser after polymer rearrangement
Mica powder, fibrous talc can be filled into the gap of derivatized polymers, form the fine and close reticular structure of arrangement,
On the basis of keeping toughness, so that the mobility and elasticity of reticular structure are improved, cost has been saved；Fatty alcohol polyoxy
The good mobility of vinyl ethers can form polyacids-polyethers block copolymer with a part of polylactic acid, it is anti-further to improve this
The hydrophobicity of water material, and molecular weight is adjusted, alleviate degradation speed.
3, the preparation method of high ductibility waterproof material of the present invention, heating in hybrid resin preparation process are concentrated under reduced pressure and have
The macromolecular structure that crosslinking is formed conducive to two kinds of polymer, improves the shock resistance of polylactic acid；In mixed glue solution preparation process,
Acetonitrile all has good dissolubility as excellent solvent, to polarity and nonpolar molecule；Double screw extruder to squeeze out
Waterproof material can play good ductility and impact resistance, meet the requirement of roof engineering material.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, all other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
A kind of high ductibility waterproof material of the present embodiment, the raw material including following weight: poly-lactic acid in high molecular weight 128g,
196 unsaturated polyester resin 52g, allyl phenoxy resin 15g, mica powder 10g, ethyl hexyl ester of epoxidized soybean oil 6g, threadiness are sliding
Mountain flour 4g, chitosan quaternary ammonium salt 2g, fatty alcohol polyoxyethylene ether 6g, heat stabilizer 0.05g, acetonitrile 95g.Wherein, thermostabilization
Agent is uniformly mixed by (3,4- ethene dioxythiophene monomer) polymer, potassium peroxydisulfate, ferric sulfate according to mass ratio 1:0.6:0.015
Afterwards, ultrasonic 5min is filtered, and microwave drying obtains under vacuum degree 500-600Pa.
The molecular weight of poly-lactic acid in high molecular weight is 120000-150000, and preparation method includes the following steps:
1) Pfansteihl 600g, the suberic acid 10g for taking 90% are added in three-necked flask after mixing, access water segregator, condensation
After pipe, blender, 0.9g p-methyl benzenesulfonic acid is added as catalyst, is warming up to 145 DEG C and is stirred to react, water segregator is discharged in time
In moisture；When generating there is no moisture, pressure in three-necked flask is reduced to 40-80Pa by the external vacuum pump of condenser pipe, heating
To 165 DEG C, it is stirred to react 20h, cooling obtains polylactic acid prepolymer；
2) polylactic acid prepolymer is added in reaction flask, epoxy resin, polylactic acid prepolymer is added after 180 DEG C of heating meltings
Molar ratio with epoxy resin is 1.1-1.2:1, and reaction flask vacuumizes, and when system starts solidification, pours out reactant and is cooled to
Room temperature obtains poly-lactic acid in high molecular weight crude product；
3) poly-lactic acid in high molecular weight crude product is ground into the slice that partial size is 6-10mm using pulverizer, reuses twin-screw
Extruder squeezes out to arrive the poly-lactic acid in high molecular weight in 180-220 DEG C.
The preparation method of the high ductibility waterproof material, comprising the following steps:
1) prepared by hybrid resin: weighing poly-lactic acid in high molecular weight, 196 unsaturated polyester resins according to above-mentioned weight, is added
In reactor, 120 DEG C of reaction 40-60min are warming up to, stop heating, after temperature is reduced to 80 DEG C, the system of being concentrated under reduced pressure into contains
Water obtains hybrid resin less than 0.6%；
2) prepared by mixed glue solution: acetonitrile is fitted into separatory funnel, is slowly added dropwise into hybrid resin, cooperative mechanical stirring
It is completely dissolved hybrid resin, adds allyl compound, ethyl hexyl ester of epoxidized soybean oil, fatty alcohol polyoxyethylene ether, heat
Stabilizer, 40-60 DEG C of stirring obtain mixed glue solution to sticky glue shape；
3) mixing is dry squeezes out: mixed glue solution, mica powder, fibrous talc, modification of chitosan being uniformly mixed, put into
The mixture of partial size 6-10mm is ground into ball mill, mixture is squeezed in 85 DEG C of vacuum drying 6-8h by double screw extruder
It forms out；Wherein five areas, engine speed 200-400rpm are arranged in twin-screw extrusion, and subsidiary engine revolving speed is 10-20rpm.Wherein,
It is 160-170 DEG C that the temperature in five areas of twin-screw extrusion, which is respectively as follows: an area, and 2nd area are 170-175 DEG C, and 3rd area are 180-185
DEG C, 4th area are 190-200 DEG C, and 5th area are 200-210 DEG C.
Embodiment 2
A kind of high ductibility waterproof material of the present embodiment, the raw material including following weight: poly-lactic acid in high molecular weight 132g,
196 unsaturated polyester resin 48g, diallyl diphenyl ether 20g, mica powder 13g, ethyl hexyl ester of epoxidized soybean oil 6g, threadiness are sliding
Mountain flour 4g, hydroxypropyl chitosan 1g, fatty alcohol polyoxyethylene ether 5g, heat stabilizer 0.08g, acetonitrile 102g.Wherein, thermostabilization
Agent is uniformly mixed by (3,4- ethene dioxythiophene monomer) polymer, potassium peroxydisulfate, ferric sulfate according to mass ratio 1:0.7:0.016
Afterwards, ultrasonic 5min is filtered, and microwave drying obtains under vacuum degree 500-600Pa.
The molecular weight of the poly-lactic acid in high molecular weight is 120000-150000, and preparation method includes the following steps: 1) taking
90% Pfansteihl 600g, suberic acid 10g is added in three-necked flask after mixing, after access water segregator, condenser pipe, blender, adds
Enter 1.3g p-methyl benzenesulfonic acid as catalyst, be warming up to 145 DEG C and be stirred to react, the moisture in water segregator is discharged in time；When not
When having moisture generation again, pressure in three-necked flask is reduced to 40-80Pa by the external vacuum pump of condenser pipe, is warming up to 165 DEG C, stirring
19h is reacted, cooling obtains polylactic acid prepolymer；
2) polylactic acid prepolymer is added in reaction flask, epoxy resin, polylactic acid prepolymer is added after 180 DEG C of heating meltings
Molar ratio with epoxy resin is 1.2:1, and reaction flask vacuumizes, and when system starts solidification, pours out reactant and is cooled to room temperature,
Obtain poly-lactic acid in high molecular weight crude product；
3) poly-lactic acid in high molecular weight crude product is ground into the slice that partial size is 6-10mm using pulverizer, reuses twin-screw
Extruder squeezes out to arrive the poly-lactic acid in high molecular weight in 180-220 DEG C.
The preparation method of the high ductibility waterproof material of the present embodiment is same as Example 1.
Embodiment 3
A kind of high ductibility waterproof material of the present embodiment, the raw material including following weight: poly-lactic acid in high molecular weight 150g,
196 unsaturated polyester resin 58g, diallyl bisphenol 16g, mica powder 9g, ethyl hexyl ester of epoxidized soybean oil 7g, fibrous talc
Powder 5g, carboxymethyl chitosan quaternary ammonium salt 3g, fatty alcohol polyoxyethylene ether 7g, heat stabilizer 0.08g, acetonitrile 106g.Wherein, hot
Stabilizer is mixed by (3,4- ethene dioxythiophene monomer) polymer, potassium peroxydisulfate, ferric sulfate according to mass ratio 1:0.8:0.016
After uniformly, ultrasonic 5min is filtered, and microwave drying obtains under vacuum degree 500-600Pa.
The molecular weight of the poly-lactic acid in high molecular weight is 120000-150000, and preparation method includes the following steps: 1) taking
90% Pfansteihl 600g, suberic acid 10g is added in three-necked flask after mixing, after access water segregator, condenser pipe, blender, adds
Enter 1.5g p-methyl benzenesulfonic acid as catalyst, be warming up to 145 DEG C and be stirred to react, the moisture in water segregator is discharged in time；When not
When having moisture generation again, pressure in three-necked flask is reduced to 40-80Pa by the external vacuum pump of condenser pipe, is warming up to 165 DEG C, stirring
21h is reacted, cooling obtains polylactic acid prepolymer；
2) polylactic acid prepolymer is added in reaction flask, epoxy resin, polylactic acid prepolymer is added after 180 DEG C of heating meltings
Molar ratio with epoxy resin is 1.15:1, and reaction flask vacuumizes, and when system starts solidification, pours out reactant and is cooled to room
Temperature obtains poly-lactic acid in high molecular weight crude product；
3) poly-lactic acid in high molecular weight crude product is ground into the slice that partial size is 6-10mm using pulverizer, reuses twin-screw
Extruder squeezes out to arrive the poly-lactic acid in high molecular weight in 180-220 DEG C.
The preparation method of the high ductibility waterproof material of the present embodiment is same as Example 1.
Embodiment 4
A kind of high ductibility waterproof material of the present embodiment, the raw material including following weight: poly-lactic acid in high molecular weight 148g,
196 unsaturated polyester resin 57g, diallyl bisphenol S 16g, mica powder 15g, ethyl hexyl ester of epoxidized soybean oil 7g, threadiness are sliding
Mountain flour 4g, chitosan quaternary ammonium salt 3g, fatty alcohol polyoxyethylene ether 9g, heat stabilizer 0.09g, acetonitrile 110g.Wherein, thermostabilization
Agent is uniformly mixed by (3,4- ethene dioxythiophene monomer) polymer, potassium peroxydisulfate, ferric sulfate according to mass ratio 1:0.8:0.018
Afterwards, ultrasonic 5min is filtered, and microwave drying obtains under vacuum degree 500-600Pa.
The molecular weight of the poly-lactic acid in high molecular weight is 120000-150000, and preparation method includes the following steps: 1) taking
90% Pfansteihl 600g, suberic acid 10g is added in three-necked flask after mixing, after access water segregator, condenser pipe, blender, adds
Enter 1.4g p-methyl benzenesulfonic acid as catalyst, be warming up to 145 DEG C and be stirred to react, the moisture in water segregator is discharged in time；When not
When having moisture generation again, pressure in three-necked flask is reduced to 40-80Pa by the external vacuum pump of condenser pipe, is warming up to 165 DEG C, stirring
22h is reacted, cooling obtains polylactic acid prepolymer；
2) polylactic acid prepolymer is added in reaction flask, epoxy resin, polylactic acid prepolymer is added after 180 DEG C of heating meltings
Molar ratio with epoxy resin is 1.18:1, and reaction flask vacuumizes, and when system starts solidification, pours out reactant and is cooled to room
Temperature obtains poly-lactic acid in high molecular weight crude product；
3) poly-lactic acid in high molecular weight crude product is ground into the slice that partial size is 6-10mm using pulverizer, reuses twin-screw
Extruder squeezes out to arrive the poly-lactic acid in high molecular weight in 180-220 DEG C.
The preparation method of the high ductibility waterproof material of the present embodiment is same as Example 1.
Embodiment 5
A kind of high ductibility waterproof material of the present embodiment, the raw material including following weight: poly-lactic acid in high molecular weight 160g,
196 unsaturated polyester resin 52g, diallyl diphenyl ether 20g, mica powder 11g, ethyl hexyl ester of epoxidized soybean oil 7g, threadiness are sliding
Mountain flour 5g, hydroxypropyl chitosan 3g, fatty alcohol polyoxyethylene ether 9g, heat stabilizer 0.12g, acetonitrile 105g.Wherein, thermostabilization
Agent is uniformly mixed by (3,4- ethene dioxythiophene monomer) polymer, potassium peroxydisulfate, ferric sulfate according to mass ratio 1:0.6:0.02
Afterwards, ultrasonic 5min is filtered, and microwave drying obtains under vacuum degree 500-600Pa.
The molecular weight of the poly-lactic acid in high molecular weight is 120000-150000, and preparation method includes the following steps: 1) taking
90% Pfansteihl 600g, suberic acid 10g is added in three-necked flask after mixing, after access water segregator, condenser pipe, blender, adds
Enter p-methyl benzenesulfonic acid as catalyst, be warming up to 145 DEG C and be stirred to react, the moisture in water segregator is discharged in time；When there is no
When moisture generates, pressure in three-necked flask is reduced to 40-80Pa, is warming up to 165 DEG C, is stirred to react by the external vacuum pump of condenser pipe
20h, cooling obtain polylactic acid prepolymer；
2) polylactic acid prepolymer is added in reaction flask, epoxy resin, polylactic acid prepolymer is added after 180 DEG C of heating meltings
Molar ratio with epoxy resin is 1.1-1.2:1, and reaction flask vacuumizes, and when system starts solidification, pours out reactant and is cooled to
Room temperature obtains poly-lactic acid in high molecular weight crude product；
3) poly-lactic acid in high molecular weight crude product is ground into the slice that partial size is 6-10mm using pulverizer, reuses twin-screw
Extruder squeezes out to arrive the poly-lactic acid in high molecular weight in 180-220 DEG C.
The preparation method of the high ductibility waterproof material of the present embodiment is same as Example 1.
Comparative example 1
Compared with Example 1, difference is to lack the addition of 196 unsaturated polyester resins this comparative example, specific to prepare
Method is as follows:
1) prepared by mixed glue solution: acetonitrile being fitted into separatory funnel, is slowly added dropwise into poly-lactic acid in high molecular weight, machine is cooperated
Tool stirring is completely dissolved poly-lactic acid in high molecular weight, adds allyl compound, ethyl hexyl ester of epoxidized soybean oil, fatty alcohol polyoxy
Vinyl ethers, heat stabilizer, 40-60 DEG C of stirring obtain mixed glue solution to sticky glue shape；
2) mixing is dry squeezes out: mixed glue solution, mica powder, fibrous talc, modification of chitosan being uniformly mixed, put into
The mixture of partial size 6-10mm is ground into ball mill, mixture is squeezed in 85 DEG C of vacuum drying 6-8h by double screw extruder
It forms out；Wherein five areas, engine speed 200-400rpm are arranged in twin-screw extrusion, and subsidiary engine revolving speed is 10-20rpm.Wherein,
It is 160-170 DEG C that the temperature in five areas of twin-screw extrusion, which is respectively as follows: an area, and 2nd area are 170-175 DEG C, and 3rd area are 180-185
DEG C, 4th area are 190-200 DEG C, and 5th area are 200-210 DEG C.
Comparative example 2
Compared with Example 1, difference is to lack the addition of poly-lactic acid in high molecular weight, specific preparation method this comparative example
It is as follows:
1) prepared by mixed glue solution: acetonitrile being fitted into separatory funnel, is slowly added dropwise into 196 unsaturated polyester resins, matches
Closing mechanical stirring is completely dissolved 196 unsaturated polyester resins, adds allyl compound, ethyl hexyl ester of epoxidized soybean oil, rouge
Fat alcohol polyoxyethylene ether, heat stabilizer, 40-60 DEG C of stirring obtain mixed glue solution to sticky glue shape；
2) mixing is dry squeezes out: mixed glue solution, mica powder, fibrous talc, modification of chitosan being uniformly mixed, put into
The mixture of partial size 6-10mm is ground into ball mill, mixture is squeezed in 85 DEG C of vacuum drying 6-8h by double screw extruder
It forms out；Wherein five areas, engine speed 200-400rpm are arranged in twin-screw extrusion, and subsidiary engine revolving speed is 10-20rpm.Wherein,
It is 160-170 DEG C that the temperature in five areas of twin-screw extrusion, which is respectively as follows: an area, and 2nd area are 170-175 DEG C, and 3rd area are 180-185
DEG C, 4th area are 190-200 DEG C, and 5th area are 200-210 DEG C.
Comparative example 3
Compared with Example 1, difference is to lack nonionic surfactant fatty alcohol polyoxyethylene ether this comparative example
Addition.
Performance test
According to professional standard JC/T1067-2008 " pitched roof waterproof material " to above-described embodiment 1-5, comparative example 1-3
The waterproof material of preparation has carried out performance test, and specific testing result is shown in Table 1:
1. waterproof material performance test results of table
As can be seen from Table 1, the waterproof material of the embodiment of the present invention is in impermeability, heat resistance, anti-impact force, extension
It is superior to the waterproof material of comparative example in rate, heat ageing elongation percentage conservation rate, illustrates waterproof performance, heat resistance, impact resistance
Ductility after energy, ductility, heat ageing is preferable.Improve poly-lactic acid in high molecular weight mechanical performance due to lacking in comparative example 1
196 unsaturated polyester resins can not be such that linear macromolecule mixes, and fine and close macromolecular structure can not be formed, so that shock resistance is strong
Degree substantially reduces；Due to lacking poly-lactic acid in high molecular weight in comparative example 2 so that poly-lactic acid in high molecular weight have tensile strength,
Impact strength, elongation percentage can not play, and shock resistance, ductility reduction are obvious；Comparative example 3 is due to lacking non-ionic surface
The addition of activating agent fatty alcohol polyoxyethylene ether is unable to improve the mobility and hydrophobicity of polymer molecule, so that waterproofness
Energy, ductility reduction are significant.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
Above content is only to structure of the invention example and explanation, affiliated those skilled in the art couple
Described specific embodiment does various modifications or additions or is substituted in a similar manner, without departing from invention
Structure or beyond the scope defined by this claim, is within the scope of protection of the invention.
Claims (7)
1. a kind of high ductibility waterproof material, which is characterized in that the raw material including following parts by weight: poly-lactic acid in high molecular weight 120-
160 parts, 40-65 parts of 196 unsaturated polyester resin, 10-22 parts of allyl compound, 6-15 parts of mica powder, epoxy soybean oleic acid
3-8 parts of monooctyl ester, 2-5 parts of fibrous talc, 1-3 parts of modification of chitosan, 3-10 parts of fatty alcohol polyoxyethylene ether, heat stabilizer
0.02-0.13 parts, 80-110 parts of acetonitrile；
The molecular weight of the poly-lactic acid in high molecular weight is 120000-150000, and preparation method includes the following steps:
1) it is added in three-necked flask after mixing 90% Pfansteihl and suberic acid according to mass ratio 60:1, it is access water segregator, cold
After solidifying pipe, blender, p-methyl benzenesulfonic acid is added as catalyst, is warming up to 145 DEG C and is stirred to react, is discharged in water segregator in time
Moisture；When generating there is no moisture, pressure in three-necked flask is reduced to 40-80Pa, is warming up to by the external vacuum pump of condenser pipe
165 DEG C, it is stirred to react 18-22h, cooling obtains polylactic acid prepolymer；
2) polylactic acid prepolymer being added in reaction flask, epoxy resin is added after 180 DEG C of heating meltings, reaction flask vacuumizes, when
When system starts solidification, pours out reactant and be cooled to room temperature, obtain poly-lactic acid in high molecular weight crude product；
3) poly-lactic acid in high molecular weight crude product is ground into the slice that partial size is 6-10mm using pulverizer, reuses twin-screw extrusion
Machine squeezes out to arrive the poly-lactic acid in high molecular weight in 180-220 DEG C.
2. high ductibility waterproof material according to claim 1, which is characterized in that the heat stabilizer is by (3,4- ethylene
Dioxythiophene monomers) polymer, potassium peroxydisulfate, ferric sulfate according to mass ratio 1:0.5-0.8:0.01-0.02 after mixing, surpass
Sound 5min is filtered, and microwave drying obtains under vacuum degree 500-600Pa.
3. high ductibility waterproof material according to claim 1, which is characterized in that the allyl compound is two allyls
One of base bisphenol-A, diallyl bisphenol S, allyl phenoxy resin, diallyl diphenyl ether or a variety of combinations.
4. high ductibility waterproof material according to claim 1, which is characterized in that the preparation of the poly-lactic acid in high molecular weight
In method, the additive amount of p-methyl benzenesulfonic acid is the 0.1-0.3% of Pfansteihl quality in step 1)；Polylactic acid prepolymer in step 2)
Molar ratio with epoxy resin is 1.1-1.2:1.
5. high ductibility waterproof material according to claim 1, which is characterized in that the modification of chitosan is hydroxypropyl base enclosure
One of glycan, chitosan quaternary ammonium salt, carboxymethyl chitosan quaternary ammonium salt or a variety of combinations.
6. a kind of preparation method of high ductibility waterproof material according to claim 1, which is characterized in that including following step
It is rapid:
1) prepared by hybrid resin: weighing poly-lactic acid in high molecular weight, 196 unsaturated polyester resins according to parts by weight, reactor is added
In, 120 DEG C of reaction 40-60min are warming up to, stops heating, after temperature is reduced to 80 DEG C, it is small to be concentrated under reduced pressure into content of water in system
In 0.6%, hybrid resin is obtained；
2) prepared by mixed glue solution: acetonitrile being fitted into separatory funnel, is slowly added dropwise into hybrid resin, cooperative mechanical stirring makes to mix
Resin is completely dissolved, and adds allyl compound, ethyl hexyl ester of epoxidized soybean oil, fatty alcohol polyoxyethylene ether, thermostabilization
Agent, 40-60 DEG C of stirring obtain mixed glue solution to sticky glue shape；
3) mixing is dry squeezes out: mixed glue solution, mica powder, fibrous talc, modification of chitosan being uniformly mixed, ball milling is put into
The mixture of partial size 6-10mm is ground into machine, mixture is extruded into 85 DEG C of vacuum drying 6-8h by double screw extruder
Type；Wherein five areas, engine speed 200-400rpm are arranged in twin-screw extrusion, and subsidiary engine revolving speed is 10-20rpm.
7. the preparation method of high ductibility waterproof material according to claim 6, which is characterized in that the double spiral shells of step 3)
Bar squeeze out five areas temperature be respectively as follows: an area be 160-170 DEG C, 2nd area be 170-175 DEG C, 3rd area be 180-185 DEG C, four
Area is 190-200 DEG C, and 5th area are 200-210 DEG C.
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| CN111675888A (en) * | 2020-07-20 | 2020-09-18 | 四川大学 | High-strength high-toughness polylactic acid-based composite material and preparation method thereof |
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