CN106589786B - One kind isomerism modified polyacetal of crosslinking agent containing L-POSS and preparation method thereof - Google Patents

Abstract

A kind of isomerism modified polyacetal of crosslinking agent containing L-POSS and preparation method thereof is related to a kind of polyformaldehyde and preparation method thereof, will first recycle POM in drying；Homemade micro- crosslinking masterbatch are smashed and ground, high-speed mixer and mixing then is put into dried recycling hard POM, micro- crosslinking masterbatch, heat stabilizer and inorganic filler by weight ratio, finally with double screw extruder extruding pelletization up to reworked material.The present invention can realize the effect of enhancing, toughening recycling POM simultaneously.On the other hand, the crosslinking agent of the structure containing L-POSS is with Si-O for inorganic kernel, and inorganic kernel can assign its good heat resistance, flame resistance, splendid water resistance, radiativity and electrical property, can play certain facilitation in process.And being introduced into for isomerism cross-linking method can make it is not necessary that compatilizer is added or keeps the toughness for regenerating POM and intensity fine in the regenerative process for recycling POM, great market popularization value.

Description

A kind of homogeneously modified polyoxymethylene containing L-POSS crosslinking agent and preparation method thereof

technical field

The invention relates to a polyoxymethylene and a preparation method thereof, in particular to a homogeneously modified polyoxymethylene containing an L-POSS crosslinking agent and a preparation method thereof.

Background technique

L-POSS cross-linking agent is a new type of silane cross-linking agent synthesized by using the synthesis method of L-POSS and silane compound reaction. The product is a derivative of silane. The active point generated by silane under the action of catalytic initiation forms an addition polymerization reaction with -LPOSS to form a crosslinking agent with double crosslinking. At the same time, because L-POSS is different from traditional organic substances, it With Si-O as the inorganic core, the inorganic core will give it good heat resistance, flame resistance, excellent water resistance, radiation and electrical properties, so the new silane crosslinking agent containing L-POSS synthesized in These performances have also been greatly improved, so this silane crosslinking agent can exist under high temperature and high radiation, and it has better performance than silane as a crosslinking agent alone, and it is also less costly than POSS directly as a crosslinking agent Many, better cross-linking effect and improved performance.

POM (English: polyformaldehyde), also known as acetal resin, has good physical, mechanical and chemical properties, especially excellent friction resistance, and is the third largest general-purpose plastic. It is suitable for making wear-reducing and wear-resistant parts, transmission parts, and chemical and instrument parts. Good performance, outstanding fatigue resistance, not easy to be corroded by chemical media, etc. In recent years, with the needs of industrial development, people have paid more and more attention to the research on the modification of polyoxymethylene. Polyoxymethylene (POM) is replacing some markets traditionally occupied by metals at a lower cost than many other engineering plastics, such as replacing zinc, brass, aluminum and steel to make many parts. Since its inception, POM has been widely used Electronics, machinery, instruments, daily light industry, automobiles, building materials, agriculture and other fields. In the application of many new fields, such as medical technology, sports equipment, etc., POM also shows a good growth trend.

On the other hand, POM is subject to strong acid corrosion, poor weather resistance, poor adhesion, thermal decomposition and softening temperature are close, small oxygen limiting index, poor impact resistance and other shortcomings limit its application, so it needs to be modified. This patent is approved by L - The preparation method of POM modified by the homogeneous cross-linking method of POSS cross-linking agent to strengthen and toughen it.

Contents of the invention

The object of the present invention is to provide a kind of homogeneous modified polyoxymethylene containing L-POSS cross-linking agent and preparation method thereof, the cross-linking agent containing L-POSS structure of the present invention is to take Si-O as the inorganic core, the inorganic core It will endow it with good heat resistance, flame resistance, excellent water resistance, radiation and electrical properties, can play a certain role in promoting the processing process, and can simultaneously achieve the effect of strengthening and toughening recycled POM.

The purpose of the present invention is achieved through the following technical solutions:

A kind of homogeneous modified polyoxymethylene containing L-POSS cross-linking agent, described L-POSS cross-linking agent adopts the method for L-POSS and silane compound reaction, and product is the derivative of silane; Its structure is:

;

Homoisomeric modified polyoxymethylene is calculated in parts by mass, and its components are:

Reclaim 100 parts of polyoxymethylene;

10-30 parts of toughening agent;

10 to 30 parts of cross-linking masterbatch;

Inorganic filler 10-20 parts;

Heat stabilizer 3 to 20 parts.

A homogeneously modified polyoxymethylene containing L-POSS cross-linking agent, the synthetic cross-linking agent includes two stages, the first is to form raw materials, and secondly, silane generates active points under catalysis so as to introduce L —POSS forming chemical reaction to prepare L-POSS-containing silane crosslinking agent.

In the homogeneously modified polyoxymethylene containing L-POSS crosslinking agent, the toughening agent is at least one of POM/POE and POM/EVA.

The homogeneously modified polyoxymethylene containing L-POSS cross-linking agent, the cross-linking masterbatch is composed of A material B material and water producing agent in three steps;

A material composition: polyoxymethylene

A new type of cross-linking agent containing L-POSS structure

Initiator (dicumyl peroxide (DCP))

B material composition: polyoxymethylene

Catalyst (dibutyltin dilaurate)

Antioxidant (Antioxidant 1010)

Water generating agent components: acid and metal oxide; the acid in the water generating agent is at least one of stearic acid and inorganic acid; the metal oxide is at least one of zinc oxide and tin oxide.

In the homogeneously modified polyoxymethylene containing L-POSS crosslinking agent, the filler is at least one of calcium carbonate and talcum powder.

In the homogeneously modified polyoxymethylene containing L-POSS crosslinking agent, the thermal stabilizer is triphenyl phosphite.

A preparation method containing L-POSS cross-linking agent homogeneously modified polyoxymethylene, the method may further comprise the steps:

A. Weigh 95 parts of material A according to the mass fraction, mix 4.5 parts of material B and put them into a twin-screw extruder to extrude and granulate, and then mix with 0.5 parts of water generating agent (stearic acid and zinc oxide 1:1) The mixture) is mixed evenly and put into a twin-screw extruder to extrude and granulate to form a cross-linked masterbatch;

B. Put the micro-crosslinked masterbatch in Part A into a universal pulverizer and then put it into a planetary ball mill to grind until the particle size of the crosslinked masterbatch reaches 10-50 μm;

C. Dry the recycled hard POM material at 80°C for 6 to 8 hours, and put the micro-crosslinked masterbatch, heat stabilizer, recycled hard POM, and inorganic filler into the high-speed mixer according to the weight ratio. 4 to 6 minutes to make it evenly mixed;

D. Add the above-mentioned uniformly mixed materials in the high-speed mixer to a twin-screw extruder with a screw length-to-diameter ratio of 36 and a rotating speed of 200r/min, and use the strong shear force of the twin-screw The average particle size of the joint masterbatch is controlled at 10-50 μm. At the same time, the cross-linking material is uniformly mixed with heat stabilizers, recycled materials and inorganic fillers. The above-mentioned mixture is extruded and granulated to obtain regenerated hard POM containing cross-linked POM.

In the preparation method of homogeneously modified polyoxymethylene containing L-POSS crosslinking agent, the screw temperature of the twin-screw extruder is controlled between 160°C and 180°C.

Advantage and effect of the present invention are:

The invention can realize the effects of strengthening and toughening recycled POM at the same time. On the other hand, the crosslinking agent containing L-POSS structure uses Si-O as the inorganic core, and the inorganic core will endow it with good heat resistance, flame resistance, excellent water resistance, radiation and electrical properties, and can It plays a certain role in promoting the processing. Moreover, the introduction of the homogeneous cross-linking method can make the regeneration process of recovered POM without adding a compatibilizer, and can also make the toughness and strength of the recycled POM very good, which is of great market promotion value.

Description of drawings

Figure 1 is the reaction equation for the synthesis of high temperature resistant crosslinking agent of L-POSS and vinyltrimethoxysilane.

Detailed ways

The present invention will be described in detail below in conjunction with examples.

Examples 1-3, the weight distribution ratio of each component in each embodiment is shown in Table 1. Weigh each component according to the ratio, mix in a high-speed mixer for 5 minutes, and discharge the material. Put the raw material of the mixture in a twin-screw extruder to make the material. The temperature of the extruder is controlled between 160°C and 180°C. The rotating speed is 200r/min. Prepare the sample and test it according to the corresponding standard (see Table 2). The performance results are shown in Table 3.

Table 1: the formula composition (part) of embodiment 1-3

Table 2: Mechanical property test standard

Test items standard test Tensile strength MPa GB/T1040.1-2006 Elongation at break % GB/T1040.1-2006 Bending strength MPa ASTM D-790 Flexural modulus MPa ASTM D-790 Notched impact strength KJ/m ² GB/T1043-93

Table 3: Mechanical property test of POM return material in embodiment 1-3

Test items Example 1 Example 2 Example 3 Tensile strength MPa 58 64 68 Elongation at break % 56% 68% 70% Bending strength MPa 80 85 90 Flexural modulus MPa 82 86 98 Notched impact strength KJ/m ² 64 89 88

For comparative examples 1-4, the weight distribution of each component in each comparative example is shown in Table 4. Weigh each component according to the ratio, mix it in a high-speed mixer for 4 minutes, and discharge the material. Put the raw material of the mixture into a twin-screw extruder to make the material. The temperature of the extruder is 160°C-180°C, and the speed is 150r/min. . Prepare the sample and test it according to the corresponding standard (see Table 2). The performance results are shown in Table 5.

Table 4: Formulation composition of comparative examples 1-4

Table 5: Mechanical property test of recovered POM in comparative examples 1-4

Test items Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Tensile strength MPa 58 64 68 80 Elongation at break % 56% 68% 70% 69% Bending strength MPa 80 85 90 85 Flexural modulus MPa 82 86 98 79 Notched impact strength KJ/m ² 64 89 88 96

From the mechanical performance test results of Examples 1-3 and Comparative Examples 1-4 in Table 3, we know that: when only using a toughening agent, the tensile performance of the material will be reduced while improving the impact performance of recycled POM; The particle size of the obtained micro-crosslinked masterbatch is crushed to 10-50 μm, and then the crosslinked material, recycled POM, inorganic filler, etc. are put into a twin-screw extruder with a large aspect ratio for shearing and mixing. At the same time, its tensile properties can also be improved; the effect of simultaneously strengthening and toughening recycled POM materials is realized. At the same time, the introduction of the cross-linking agent containing L-POSS structure is also helpful to the processing process, and has an efficient cross-linking effect.

The present invention has been further described above through specific embodiments, but these embodiments are only exemplary and do not constitute any limitation to the protection scope of the present invention. Those skilled in the art understand that without departing from the spirit and scope of protection of the present invention, various equivalent replacements, modifications or improvements can be made to the technical solutions and implementations of the present invention, all of which should fall under the protection of the present invention. within range. The protection scope of the present invention shall be determined by the appended claims.

Claims (6)

1. A homogeneous modified polyoxymethylene containing L-POSS cross-linking agent, it is characterized in that, described L-POSS cross-linking agent adopts the method that L-POSS and silane compound react, and product is the derivation of silane matter; its structure is: ; Homoisomeric modified polyoxymethylene is calculated in parts by mass, and its components are: Reclaim 100 parts of polyoxymethylene; 10-30 parts of toughening agent; 10-30 parts of cross-linking masterbatch; 10-20 parts of inorganic filler; Heat stabilizer 3 to 20 parts; The cross-linking masterbatch is composed of A material, B material and water generating agent in three steps; A material composition: polyoxymethylene L-POSS cross-linking agent Initiator, described initiator is dicumyl peroxide DCP B material composition: polyoxymethylene Catalyst, described catalyst is dibutyltin dilaurate Antioxidant, described antioxidant is antioxidant 1010 Water generating agent components: acid and metal oxide; the acid in the water generating agent is at least one of stearic acid and inorganic acid; the metal oxide is at least one of zinc oxide and tin oxide; The L-POSS cross-linking agent includes two stages, firstly, raw materials are formed, and secondly, under the action of catalysis, silane generates active points to introduce L-POSS to form a chemical reaction to prepare the L-POSS-containing cross-linking agent. 2. a kind of homogeneously modified polyoxymethylene containing L-POSS cross-linking agent according to claim 1, is characterized in that, described toughening agent is at least one in POM/POE, POM/EVA. 3. a kind of homogeneously modified polyoxymethylene containing L-POSS cross-linking agent according to claim 1, is characterized in that, described filler is at least one in calcium carbonate, talcum powder. 4. A kind of homogeneous modified polyoxymethylene containing L-POSS crosslinking agent according to claim 1, is characterized in that, described thermal stabilizer is triphenyl phosphite. 5. a kind of preparation method containing L-POSS linking agent homogeneous modification polyoxymethylene according to claim 1, is characterized in that, described method comprises the following steps: A. Weigh 95 parts of material A according to the mass fraction, mix 4.5 parts of material B and put it into a twin-screw extruder to extrude and granulate, then mix it with 0.5 part of water producing agent, mix evenly and put it into the twin-screw extruder Extruding granulation to form a cross-linked masterbatch, the water producing agent is a mixture of 1:1 stearic acid and zinc oxide; B. Put the crosslinked masterbatch in step A into a universal pulverizer and then put it into a planetary ball mill to grind until the particle size of the crosslinked masterbatch reaches 10-50 μm; C. Air-dry the recycled polyoxymethylene material at 80°C for 6-8 hours, put the cross-linking masterbatch, heat stabilizer, recycled polyoxymethylene and inorganic filler into the high-speed mixer according to the weight ratio and mix for 4-6 minutes to make it evenly mixed; D. Add the above-mentioned uniformly mixed materials in the high-speed mixer to a twin-screw extruder with a screw length-to-diameter ratio of 36 and a rotating speed of 200r/min, and use the strong shear force of the twin-screw in the molten state to crosslink The average particle size of the masterbatch is controlled at 10-50μm. At the same time, the cross-linked masterbatch is mixed with heat stabilizer, recycled polyoxymethylene and inorganic filler evenly, and the above-mentioned mixture is extruded and granulated to obtain a homogeneous cross-linking agent containing L-POSS. Isomerized modified polyoxymethylene. 6. A method for preparing homogeneously modified polyoxymethylene containing L-POSS crosslinking agent according to claim 5, characterized in that, the screw temperature of the twin-screw extruder is controlled at 160°C-180°C between.